KR20200014377A - Polymerizable liquid crystal compound, polymerizable liquid crystal composition, optically anisotropic film, optical film, polarizing plate, and image display device - Google Patents

Abstract

An object of the present invention is to provide a polymerizable liquid crystal compound, a polymerizable liquid crystal composition, an optically anisotropic film, an optical film, a polarizing plate, and an image display device which are used for forming an optically anisotropic film having excellent reverse wavelength dispersion. The polymeric liquid crystal compound of this invention is a polymeric liquid crystal compound represented by following formula (1), and is a polymeric liquid crystal compound whose ClogP value of group represented by Ar in following formula (1) is 3.5 or less.

Description

Polymerizable liquid crystal compound, polymerizable liquid crystal composition, optically anisotropic film, optical film, polarizing plate, and image display device

The present invention relates to a polymerizable liquid crystal compound, a polymerizable liquid crystal composition, an optically anisotropic film, an optical film, a polarizing plate, and an image display device.

Since the polymerizable compound exhibiting reverse wavelength dispersion has the characteristics of being able to accurately convert a light wavelength in a wide wavelength range, and having a high refractive index, it is possible to thin a retardation film. Is being studied.

In addition, generally, a T-type molecular design guideline is adopted as the polymerizable compound exhibiting reverse wavelength dispersion, and it is required to shorten the wavelength of the long axis of the molecule and to lengthen the short wavelength of the axis located at the center of the molecule. .

For this reason, it is known to use the cycloalkylene skeleton which does not have an absorption wavelength for the connection of the short axis skeleton (henceforth "reverse wavelength dispersion expression part") located in the center of a molecule, and the molecular long axis (for example, , Patent Documents 1 to 4).

Patent Document 1: Japanese Unexamined Patent Publication No. 2008-273925 Patent Document 2: Japanese Unexamined Patent Publication No. 2010-031223 Patent Document 3: International Publication No. 2014/010325 Patent Document 4: Japanese Unexamined Patent Publication No. 2016-081035

MEANS TO SOLVE THE PROBLEM The present inventors examined patent documents 1-4, and according to the polymerization conditions, such as the kind of polymeric compound, the kind of polymerization initiator, and hardening temperature, the optically anisotropic film formed may be inferior to reverse wavelength dispersion. Made it clear.

Therefore, an object of this invention is to provide the polymeric liquid crystal compound, polymeric liquid crystal composition, optically anisotropic film, optical film, a polarizing plate, and an image display apparatus which are used for formation of the optically anisotropic film excellent in reverse wavelength dispersion.

MEANS TO SOLVE THE PROBLEM As a result of earnestly examining in order to achieve the said subject, it turned out that the aromatic ring which comprises the reverse wavelength dispersion expression part meets a predetermined ClogP value, and also puts a predetermined | prescribed frame | skeleton in the long-axis direction of the molecule centered on the reverse wavelength dispersion expression part. It was discovered that the reverse wavelength dispersion of the optically anisotropic film formed also improves by making it have, and completed this invention.

That is, it discovered that the said subject can be achieved by the following structures.

[1] A polymerizable liquid crystal compound, wherein the ClogP value of a group represented by Ar in Formula (1) described later is 3.5 or less, as the polymerizable liquid crystal compound represented by Formula (1) described later.

[2] The polymerizable liquid crystal compound according to [1], wherein D ¹ and D ² in Formula (1) described later represent -O-, and D ³ and D ⁴ represent -O-CO-.

[3] A polymerizable liquid crystal composition containing the polymerizable liquid crystal compound according to [1] or [2].

[4] The polymerizable liquid crystal composition according to [3], further comprising a polymerizable compound having at least one polymerizable group different from the polymerizable liquid crystal compound.

[5] An optically anisotropic film obtained by polymerizing the polymerizable liquid crystal composition according to [3] or [4].

[6] An optical film having an optically anisotropic film as described in [5].

[7] A polarizing plate having the optical film according to [6] and a polarizer.

[8] An image display device having the optical film according to [6] or the polarizing plate according to [7].

According to this invention, the polymeric liquid crystal compound, polymeric liquid crystal composition, optically anisotropic film, optical film, polarizing plate, and image display apparatus which are used for formation of the optically anisotropic film excellent in reverse wavelength dispersion can be provided.

1: A is typical sectional drawing which shows an example of the optical film of this invention.
It is typical sectional drawing which shows an example of the optical film of this invention.
It is typical sectional drawing which shows an example of the optical film of this invention.

EMBODIMENT OF THE INVENTION Hereinafter, this invention is demonstrated in detail.

Although description of the element | module described below may be made | formed based on typical embodiment of this invention, this invention is not limited to such embodiment.

In addition, in this specification, the numerical range represented using "-" means the range which includes the numerical value described before and after "-" as a lower limit and an upper limit.

In the present specification, a divalent group represented (e.g., -O-CO-) bond direction is not particularly limited, for D ³ is -O-CO- in formula (1) to be described later g In this case, when the position at the SP ¹ side is * 1 and the position at the cyclohexane ring side is * 2, D ³ may be * 1-O-CO- * 2, and * 1- CO-O- * 2 may be sufficient.

[Polymerizable Liquid Crystal Compound]

The polymerizable liquid crystal compound of the present invention is a compound represented by the following formula (1).

[Formula 1]

Moreover, the ClogP value of the group represented by Ar in the said Formula (1) of the polymeric liquid crystal compound of this invention is 3.5 or less.

Here, the ClogP value is a value obtained by calculating the common logarithm logP of the partition coefficient P for 1-octanol and water. Although a well-known thing can be used about the method and software used for calculation of a ClogP value, unless otherwise demonstrated, it uses the ClogP program introduced in ChemBioDraw Ultra 13.0 of Cambridge soft in this invention.

In the present invention, as described above, the ClogP value of the group (aromatic ring) represented by Ar in the formula (1) is 3.5 or less, and cyclohexane rings are formed in the long axis direction of the molecule centered on Ar. By having the skeleton connected by single bond, the reverse wavelength dispersion of the optically anisotropic film formed improves.

Although this is not clear in detail, the present inventors guess as follows.

That is, the compound represented by the above formula (1) has a structure in which cyclohexane rings are connected in a single bond in the molecular long axis direction, and does not have a benzene ring in the molecular long axis direction, thereby achieving shorter wavelength. Since it exists, the reverse wavelength dispersion of the optically anisotropic film formed is considered to have improved.

Hereinafter, the structure of said Formula (1) is demonstrated in detail about the polymeric liquid crystal compound of this invention.

As mentioned above, the polymeric liquid crystal compound of this invention is a polymeric liquid crystal compound represented by following formula (1).

[Formula 2]

In said formula (1), D <^1> and D <^2> respectively independently represent -O-, -S-, or -NR <^1> -, D <^3> and D <^4> respectively independently represent a single bond and -O-CO -, -C (= S) O-, -CR ¹ R ^2- , -CR ¹ R ² -CR ³ R ^4- , -O-CR ¹ R ^2- , -CR ¹ R ² -O-CR ³ R ^4- , -CO-O-CR ¹ R ^2- , -O-CO-CR ¹ R ^2- , -CR ¹ R ² -O-CO-CR ³ R ^4- , -CR ¹ R ² -CO-O -CR ³ R ^4- , -NR ¹ -CR ² R ^3- , or -CO-NR ^1- . R ¹ , R ² , R ^3, and R ⁴ each independently represent a hydrogen atom, a fluorine atom, or an alkyl group having 1 to 4 carbon atoms.

In the formula (1), SP ¹ and SP ² each independently constitute a single bond, a linear or branched alkylene group having 1 to 12 carbon atoms, or a linear or branched alkylene group having 1 to 12 carbon atoms. At least one of -CH ₂ -to represent a divalent linking group substituted with —O—, —S—, —NH—, —N (Q) —, or —CO—, and Q represents a substituent.

In addition, in said Formula (1), L <^1> and L <^2> represent a monovalent organic group each independently, and at least one of L <^1> and L <^2> represents a polymeric group. However, when Ar is an aromatic ring represented by Formula (Ar-3) described later, at least one of L ¹ and L ² and L ³ and L ⁴ in Formula (Ar-3) described later represents a polymerizable group.

In Formula (1), Ar represents any of aromatic rings selected from the group consisting of groups represented by formulas (Ar-1) to (Ar-5) described later.

The formula (1) of, SP ¹ and the alkylene group a linear or branched having 1 to 12 carbon atoms represented by SP ^2, for example a methylene group, an ethylene group, a propylene group, a butyl group, a pentylene group, a hexylene group, Methyl hexylene group, heptylene group, etc. are mentioned suitably.

Moreover, as said monovalent organic group which L <^1> and L <^2> represent in said formula (1), an alkyl group, an aryl group, heteroaryl group, etc. are mentioned, for example. Although an alkyl group may be linear, branched, or cyclic, linear is preferable. 1-30 are preferable, as for carbon number of an alkyl group, 1-20 are more preferable, and 1-10 are more preferable. Moreover, although monocyclic or polycyclic may be sufficient as an aryl group, monocyclic is preferable. 6-25 are preferable and, as for carbon number of an aryl group, 6-10 are more preferable. In addition, the heteroaryl group may be monocyclic or polycyclic. As for the number of the hetero atoms which comprise a heteroaryl group, 1-3 are preferable. As for the hetero atom which comprises a heteroaryl group, a nitrogen atom, a sulfur atom, and an oxygen atom are preferable. 6-18 are preferable and, as for carbon number of a heteroaryl group, 6-12 are more preferable. Moreover, an alkyl group, an aryl group, and heteroaryl group may be unsubstituted, and may have a substituent. As a substituent, the same thing as the substituent which Y <^1> in Formula (Ar-1) mentioned later may have is mentioned.

In addition, although the polymeric group which at least one of L <^1> and L <^2> represents in said Formula (1) is not specifically limited, The polymeric group which can be radically polymerized or cationic polymerization is preferable.

As a radically polymerizable group, generally known radically polymerizable group can be used, Acryloyl group or methacryloyl group is mentioned as a suitable thing. In this case, it is known that acryloyl group is generally fast in polymerization rate, and although acryloyl group is preferable from a viewpoint of productivity improvement, methacryloyl group can be used similarly as a polymerizable group.

As the cationically polymerizable group, generally known cation polymerizable groups can be used, and specifically, an alicyclic ether group, a cyclic acetal group, a cyclic lactone group, a cyclic thiether group, a spiro ortho ester group, a vinyloxy group, or the like can be used. Can be mentioned. Especially, alicyclic ether group or vinyloxy group is suitable, and an epoxy group, an oxetanyl group, or a vinyloxy group is especially preferable.

The following is mentioned as an example of an especially preferable polymeric group.

[Formula 3]

In Formula (1), Ar represents any of aromatic rings selected from the group consisting of groups represented by the following formulas (Ar-1) to (Ar-5). In addition, * represents a coupling | bonding position with D <^1> or D <^2> in said Formula (1) in following formula (Ar-1)-(Ar-5).

[Formula 4]

In the formula (Ar-1), Q ¹ represents N or CH, Q ² represents -S-, -O-, or -N (R ⁵ )-, and R ⁵ represents hydrogen. The atom or C1-C6 alkyl group is shown, Y <^1> represents the C6-C12 aromatic hydrocarbon group or C3-C12 aromatic heterocyclic group which may have a substituent.

Specific examples of the alkyl group having 1 to 6 carbon atoms represented by R ⁵ include methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group and n- A pentyl group, n-hexyl group, etc. are mentioned.

As a C6-C12 aromatic hydrocarbon group which Y <^1> represents, aryl groups, such as a phenyl group, 2, 6- diethylphenyl group, a naphthyl group, are mentioned, for example.

As a C3-C12 aromatic heterocyclic group which Y <^1> represents, heteroaryl groups, such as a thienyl group, thiazolyl group, a furyl group, a pyridyl group, are mentioned, for example.

Moreover, as a substituent which Y <^1> may have, an alkyl group, an alkoxy group, a halogen atom, etc. are mentioned, for example.

As an alkyl group, a C1-C18 linear, branched or cyclic alkyl group is preferable, for example, A C1-C8 alkyl group (for example, a methyl group, an ethyl group, a propyl group, an isopropyl group, n-butyl group) is preferable. , Isobutyl group, sec-butyl group, t-butyl group, cyclohexyl group, etc.) are more preferable, It is more preferable that it is a C1-C4 alkyl group, It is especially preferable that it is a methyl group or an ethyl group.

As an alkoxy group, a C1-C18 alkoxy group is preferable, for example, and a C1-C8 alkoxy group (for example, a methoxy group, an ethoxy group, n-butoxy group, a methoxyethoxy group, etc.) is more preferable. It is more preferable that it is a C1-C4 alkoxy group, and it is especially preferable that it is a methoxy group or an ethoxy group.

As a halogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom etc. are mentioned, for example, Especially, it is preferable that they are a fluorine atom and a chlorine atom.

In addition, in said formula (Ar-1)-(Ar-5), Z <^1> , Z <^2> and Z <^3> respectively independently represent a hydrogen atom, a C1-C20 monovalent aliphatic hydrocarbon group, and C3-C20 A monovalent alicyclic hydrocarbon group, a C6-C20 monovalent aromatic hydrocarbon group, a halogen atom, a cyano group, a nitro group, -OR ⁶ , -NR ⁷ R ⁸ , or -SR ⁹ is represented, and R ⁶ to R ⁹ each independently represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and Z ¹ and Z ² may be bonded to each other to form an aromatic ring.

As a C1-C20 monovalent aliphatic hydrocarbon group, a C1-C15 alkyl group is preferable, A C1-C8 alkyl group is more preferable, A methyl group, an ethyl group, an isopropyl group, and a tert-pentyl group ( 1,1-dimethylpropyl group), tert-butyl group, 1,1-dimethyl-3,3-dimethyl-butyl group are more preferable, and a methyl group, an ethyl group, and a tert-butyl group are especially preferable.

As a C3-C20 monovalent alicyclic hydrocarbon group, For example, cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group, cyclodecyl group, methylcyclohexyl group, Monocyclic saturated hydrocarbon groups such as ethylcyclohexyl group; Monocyclic, such as cyclobutenyl group, cyclopentenyl group, cyclohexenyl group, cycloheptenyl group, cyclooctenyl group, cyclodecenyl group, cyclopentadienyl group, cyclohexadieneyl group, cyclooctadieneyl group, and cyclodecadiene Unsaturated hydrocarbon groups; Bicyclo [2.2.1] heptyl group, bicyclo [2.2.2] octyl group, tricyclo [5.2.1.0 ^2,6 ] decyl group, tricyclo [3.3.1.1 ^3,7 ] decyl group, tetracyclo [6.2 .1.1 ^3,6 .0 ^2,7 ] polycyclic saturated hydrocarbon groups such as dodecyl group and adamantyl group.

Specifically as a C6-C20 monovalent aromatic hydrocarbon group, a phenyl group, 2, 6- diethylphenyl group, a naphthyl group, a biphenyl group etc. are mentioned, for example, A C6-C12 aryl group (especially a phenyl group) Is preferred.

As a halogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom etc. are mentioned, for example, Especially, it is preferable that they are a fluorine atom, a chlorine atom, and a bromine atom.

In addition, as a C1-C6 alkyl group which R <^6> -R <^8> represents, a methyl group, an ethyl group, a propyl group, an isopropyl group, n-butyl group, an isobutyl group, sec-butyl group, tert- specifically, is mentioned, for example. A butyl group, n-pentyl group, n-hexyl group, etc. are mentioned.

In addition, in said Formula (Ar-2) and (Ar-3), A <^1> and A <^2> are group which consists of -O-, -N (R <^10> )-, -S-, and -CO- each independently. The group chosen from, and R <^10> represents a hydrogen atom or a substituent.

As a substituent which R <^10> represents, the thing similar to the substituent which Y <^1> in said Formula (Ar-1) may have is mentioned.

In addition, in said formula (Ar-2), X represents the nonmetallic atom of group 14-16 which the hydrogen atom or the substituent may couple | bond.

Moreover, as a nonmetallic atom of group 14-16 which X represents, an oxygen atom, a sulfur atom, the nitrogen atom which has a substituent, and the carbon atom which has a substituent are mentioned, As a substituent, an alkyl group specifically, is mentioned, for example. , An alkoxy group, an alkyl substituted alkoxy group, a cyclic alkyl group, an aryl group (for example, a phenyl group, a naphthyl group, etc.), a cyano group, an amino group, a nitro group, an alkylcarbonyl group, a sulfo group, a hydroxyl group, and the like.

In the formula (Ar-3), D ⁵ and D ⁶ each independently represent a single bond, -CO-O-, -C (= S) O-, -CR ¹ R ^2- , and -CR ¹ R ² -CR ³ R ^4- , -O-CR ¹ R ^2- , -CR ¹ R ² -O-CR ³ R ^4- , -CO-O-CR ¹ R ^2- , -O-CO-CR ¹ R ^2- , -CR ¹ R ² -O-CO-CR ³ R ^4- , -CR ¹ R ² -CO-O-CR ³ R ^4- , -NR ¹ -CR ² R ^3- , or -CO-NR ¹ -is indicated. R ¹ , R ² , R ^3, and R ⁴ each independently represent a hydrogen atom, a fluorine atom, or an alkyl group having 1 to 4 carbon atoms.

Further, in the formula (Ar-3) of the, SP ³ and SP ⁴ are each independently a single bond, having from 1 to 12 carbon atoms in the straight-chain or branched alkylene group, or a straight-chain or alkylene on the branches of 1 to 12 carbon atoms on the At least one of -CH ₂ -constituting the group represents a divalent linking group substituted with -O-, -S-, -NH-, -N (Q)-, or -CO-, and Q represents a substituent. As a substituent, the same thing as the substituent which Y <^1> in said Formula (Ar-1) may have is mentioned.

In addition, in said Formula (Ar-3), L <^3> and L <^4> represent a monovalent organic group each independently, and at least one of L <^3> and L <^4> and L <^1> and L <^2> in said Formula (1) is a polymeric group Indicates.

As monovalent organic group, the thing similar to what was demonstrated in L <^1> and L <^2> in said Formula (1) is mentioned.

Moreover, as a polymeric group, the thing similar to what was demonstrated in L <^1> and L <^2> in said Formula (1) is mentioned.

Moreover, in said Formula (Ar-4)-(Ar-5), Ax represents the C2-C30 organic group which has at least 1 aromatic ring selected from the group which consists of an aromatic hydrocarbon ring and an aromatic heterocycle.

Moreover, in said Formula (Ar-4)-(Ar-5), Ay is chosen from the group which consists of a hydrogen atom, the C1-C12 alkyl group which may have a substituent, or an aromatic hydrocarbon ring and an aromatic heterocycle. An organic group having 2 to 30 carbon atoms having at least one aromatic ring is represented.

Here, the aromatic ring in Ax and Ay may have a substituent, and Ax and Ay may combine and form the ring.

Moreover, Q <^3> represents the hydrogen atom or the C1-C6 alkyl group which may have a substituent.

Examples of Ax and Ay include those described in paragraphs [0039] to [0095] of Patent Document 3 (International Publication No. 2014/010325).

Moreover, as a C1-C6 alkyl group which Q <^3> represents, a methyl group, an ethyl group, a propyl group, an isopropyl group, n-butyl group, an isobutyl group, sec-butyl group, tert- butyl group, n- pen and the like group, and n- hexyl group, can be given as the substituent, the same as the substituent which may the Y ¹ in the formula (Ar-1) has.

In the present invention, as the polymerizable compound represented by Formula (1), D ¹ and D ² in Formula (1) represent -O- and D ³ and D ⁴ are-for the reason of easy synthesis. It is preferable that it is a compound which shows O-CO-.

Moreover, in this invention, as a polymeric compound represented by said Formula (1), the compound represented by following formula (I) and (II) is mentioned, for example, Specifically, following formula (I) and (II) As K (side chain structure), the compound which has a side chain structure shown to following Table 1 and Table 2 is mentioned, respectively.

In addition, in following Table 1 and Table 2, "*" shown by K side chain structure shows the coupling | bonding position with an aromatic ring.

In addition, in the following description, the compound represented by following formula (I) and having group shown by 1-1 of following Table 1 is represented by "compound (I-1-1)", and has a compound with other structural formula and group The same method is used for. For example, the compound represented by following formula (II) and having group shown by 2-3 in following Table 2 can be described as "compound (II-2-3)."

In the side chain structures represented by 1-2 in Table 1 and 2-2 in Table 2 below, the groups adjacent to the acryloyloxy group and the methacryloyl group are each a propylene group (a group in which a methyl group is substituted with an ethylene group). Represents a mixture of positional isomers differing in the position of the methyl group.

[Formula 5]

TABLE 1

TABLE 2

In this invention, it is preferable that the ClogP value of the group represented by Ar in said formula (1) is 2.5 or more, and it is more preferable that it is 2.7 or more because the wet heat durability of the formed optically anisotropic film becomes favorable.

In addition,, Z ^1, and of In the formula (1) for the reason becomes easy to design the ClogP value of the group represented by in Ar to 3.5 or less, the above formula (Ar-1) ~ (Ar-5) in the present invention It is preferable that either one of Z ² is a hydrogen atom, the other is a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, one of Z ¹ and Z ² is a hydrogen atom, and the other is a hydrogen atom or a methyl group. desirable.

[Synthesis method of polymerizable liquid crystal compound]

Although the synthesis | combining method of the polymerizable liquid crystal compound of this invention is not specifically limited, For example, the 1st esterification process which makes the compound represented by following formula (2) and the compound represented by following formula (3) react, and produces | generates a phenolic compound. and,

The method which has a 2nd esterification process which makes the phenol reactant obtained by the 1st esterification process and the compound represented by following formula (4) react, and obtains the polymeric liquid crystal compound of this invention is mentioned.

In addition, when the compound represented by following formula (3) and the compound represented by following formula (4) are the same compound, the compound represented by following formula (2) and the compound represented by following formula (3) are made to react, A polymerizable liquid crystal compound can be synthesized.

Moreover, as a mixture of the some polymeric liquid crystal compound from which the terminal structure differs by mixing and reacting the compound represented by following formula (2), the compound represented by following formula (3), and the compound represented by following formula (4). You can get it.

Moreover, when the compound represented by following formula (2) may use 2 or more types together, and when using 2 or more types of compounds represented by following formula (2), the polymerizable liquid crystal compound of this invention expresses reverse wavelength dispersion expression. Ar structure corresponding to a part can be obtained as a mixture of several polymerizable liquid crystal compound.

[Formula 6]

Here, Ar in said Formula (2), L <^1> , SP <^1> and D <^3> in said Formula (3), and L <^2> , SP <^2> and D <^4> in said Formula (4) are all to said Formula (1). Same as described.

Further, the polymerizable liquid crystal compound obtained in the above-described synthesis method, of polymerizable liquid crystal compound represented by the formula (1), wherein the formula D ¹ and D ² in (1) represents an -O-, D ³ and also D ⁴ is a compound showing an -O-CO-.

<Esterification Reaction>

The compound represented by said Formula (2) in the case where the above-mentioned 1st esterification process and 2nd esterification process, the compound represented by said Formula (3), and the compound represented by said Formula (4) are the same compound, and the said As for the reaction process, the reaction conditions of the compound represented by Formula (3) are not specifically limited, Conventionally well-known reaction conditions of esterification can be employ | adopted suitably.

For example, it is preferable that reaction temperature is performed at -10-40 degreeC, It is more preferable to be performed at -5-30 degreeC, It is still more preferable to be performed at 0-20 degreeC.

Moreover, it is preferable to carry out reaction time for 10 minutes-24 hours, It is more preferable to carry out for 1 hour-10 hours, It is more preferable to carry out for 1 hour-8 hours.

[Polymerizable Liquid Crystal Composition]

The polymerizable liquid crystal composition of the present invention is a polymerizable liquid crystal composition containing the polymerizable liquid crystal compound of the present invention described above, in addition to the polymerizable liquid crystal compound of the present invention, other polymerizable compounds, polymerization initiators, solvents, and the like described later. It may contain.

[Other Polymerizable Compounds]

The polymeric liquid crystal composition of this invention may contain the other polymeric compound which has one or more polymeric groups other than the polymeric liquid crystal compound of this invention mentioned above.

Here, the polymeric group which another polymeric compound has is not specifically limited, For example, a (meth) acryloyl group, a vinyl group, a styryl group, an allyl group, etc. are mentioned. Especially, it is preferable to have a (meth) acryloyl group.

As another polymeric compound, from the reason which the durability of the optically anisotropic film formed improves more, it is preferable that it is another polymeric compound which has 1-4 polymerizable groups, and it is more preferable that it is another polymeric compound which has two polymeric groups. Do.

As another polymeric compound, the compound of Paragraph [0073]-[0074] of Unexamined-Japanese-Patent No. 2016-053709 is mentioned.

Moreover, as another polymeric compound, the compound represented by Formula (M1), (M2), (M3) as described in Paragraph [0030]-[0033] of Unexamined-Japanese-Patent No. 2014-077068 is mentioned, More specifically, And the specific examples described in the paragraphs [0046] to [0055] of the same publication.

Moreover, as another polymeric compound, the thing of the structure of Formula (1)-(3) described in Unexamined-Japanese-Patent No. 2014-198814 can also be used preferably, More specifically, it is the same publication as [0020]-[0035] ], [0042] to [0050], and the specific examples described in the paragraphs [0056] to [0057].

[Polymerization initiator]

It is preferable that the polymeric liquid crystal composition of this invention contains the polymerization initiator.

It is preferable that the polymerization initiator to be used is a photoinitiator which can start a polymerization reaction by ultraviolet irradiation.

As a photoinitiator, For example, the (alpha) -carbonyl compound (it describes each specification of US Pat. No. 23,684,1, 2367670), an acyloinether (described in US Pat. No. 2448828), (alpha) -hydrocarbon substituted aromatic acyl A loin compound (described in US Patent No. 2722512), a multinuclear quinone compound (US Patent Publication No. 3046127, described in each specification of the same 2951758), a combination of a triarylimidazole dimer with p-aminophenyl ketone (US patent Publication No. 3549367), Acridine and Phenazine Compounds (Japanese Laid-Open Patent Publication No. 60-105667, US Patent Publication No. 4239850) and Oxadiazole Compounds (US Patent Publication No. 4212970), Acyl Force A pin oxide compound (Japanese Unexamined-Japanese-Patent No. 63-040799, Unexamined-Japanese-Patent No. 5-029234, Unexamined-Japanese-Patent No. 10-095788, and Unexamined-Japanese-Patent No. 10-029997) etc. are mentioned. .

In the present invention, for the reason that the durability of the optically anisotropic film formed is further improved, the polymerization initiator is preferably an oxime type polymerization initiator, and more preferably a polymerization initiator represented by the following formula (PI).

[Formula 7]

In said formula (PI), X <^2> represents a hydrogen atom or a halogen atom.

In the formula (PI), Ar ² represents a divalent aromatic group, and D ⁷ represents a divalent organic group having 1 to 12 carbon atoms.

In addition, in said formula (PI), R <^11> represents a C1-C12 alkyl group and Y <^2> represents a monovalent organic group.

As said halogen atom which X <^2> represents in said formula (PI), a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, etc. are mentioned, for example, It is preferable that it is a chlorine atom especially.

In addition, in said formula (PI), Ar <^2> represents As a bivalent aromatic group, For example, aromatic hydrocarbon rings, such as a benzene ring, a naphthalene ring, anthracene ring, and a phenanthroline ring; And divalent groups having aromatic heterocycles such as a furan ring, a pyrrole ring, a thiophene ring, a pyridine ring, a thiazole ring, and a benzothiazole ring.

Moreover, as said C1-C12 divalent organic group which D <^7> represents in said Formula (PI), a C1-C12 linear or branched alkylene group is mentioned, specifically, a methylene group, Ethylene group, a propylene group, etc. are mentioned suitably.

Moreover, specifically, as a C1-C12 alkyl group which R <^11> represents in said Formula (PI), a methyl group, an ethyl group, a propyl group, etc. are mentioned suitably, for example.

In addition, as the above formula (PI), Y 1 represents a monovalent organic group ² includes, for example, a functional group containing a benzophenone skeleton _{((C 6 H 5) 2} CO). Specifically, like the group represented by the following formula (PIa) and the following formula (PIb), a functional group containing a benzophenone skeleton in which the terminal benzene ring is unsubstituted or monosubstituted is preferable. In addition, in following formula (PIa) and following formula (PIb), * represents a coupling | bonding position, ie, the coupling | bonding position with the carbon atom of the carbonyl group in the said Formula (PI).

[Formula 8]

As an oxime type polymerization initiator represented by said formula (PI), the compound represented by a following formula (PI-1), the compound represented by a following formula (PI-2), etc. are mentioned, for example.

[Formula 9]

In this invention, although content of the said polymerization initiator is not specifically limited, It is preferable that it is 0.01-20 mass% of solid content of a polymeric liquid crystal composition, and it is more preferable that it is 0.5-5 mass%.

〔menstruum〕

It is preferable that the polymeric liquid crystal composition of this invention contains a solvent from a viewpoint of the workability etc. which form an optically anisotropic film.

Specifically as a solvent, For example, ketones (for example, acetone, 2-butanone, methyl isobutyl ketone, cyclohexanone, cyclopentanone, etc.), ethers (for example, dioxane, tetrahydrofuran) Etc.), aliphatic hydrocarbons (e.g., hexane), alicyclic hydrocarbons (e.g., cyclohexane, etc.), aromatic hydrocarbons (e.g., toluene, xylene, trimethylbenzene Etc.), halogenated carbons (e.g., dichloromethane, dichloroethane, dichlorobenzene, chlorotoluene, etc.), esters (e.g., methyl acetate, ethyl acetate, butyl acetate, etc.), water , Alcohols (for example, ethanol, isopropanol, butanol, cyclohexanol, etc.), cellosolves (for example, methyl cellosolve, ethyl cellosolve, etc.), cellosolve acetates, sulfoxides (For example, dimethyl sulfoxide, etc.), flaxseed Drew (for example, dimethylformamide, dimethylacetamide, etc.) etc. are mentioned, These may be used individually by 1 type, and may use 2 or more types together.

[Leveling agent]

It is preferable that the polymeric liquid crystal composition of this invention contains a leveling agent from a viewpoint which keeps the surface of an optically anisotropic film smooth and makes orientation control easy.

As such a leveling agent, it is preferable that it is a fluorine-type leveling agent or a silicon-type leveling agent because of the high leveling effect with respect to addition amount, and it is more preferable that it is a fluorine-type leveling agent from a viewpoint which is hard to produce an exudation (bloom, bleed).

As a leveling agent, the compound specifically, described, for example in description of Paragraph [0079]-[0102] of Unexamined-Japanese-Patent No. 2007-069471, and the compound represented by General formula (I) of Unexamined-Japanese-Patent No. 2013-047204. (Particularly, compounds described in paragraphs [0020] to [0032]), compounds represented by general formula (I) described in JP 2012-211306 A (particularly compounds described in paragraphs [0022] to [0029]) Liquid crystal alignment promoter represented by General Formula (I) described in Patent Publication No. 2002-129162 (in particular, the compounds described in [0076] to [0078] and [0082] to [0084]), and Japanese Unexamined Patent Publication No. 2005-099248 The compound represented by general formula (I), (II), and (III) which were described (especially the compound of paragraphs [0092]-[0096]) etc. are mentioned. Moreover, you may have a function as an orientation controlling agent mentioned later.

[Orientation control agent]

The polymeric liquid crystal composition of this invention can contain an orientation controlling agent as needed.

By the orientation control agent, in addition to the homogeneous orientation, various orientation states such as homeotropic orientation (vertical orientation), oblique orientation, hybrid orientation, and cholesteric orientation can be formed, and specific orientation states are more uniform and It can be realized with precise control.

As an orientation control agent which promotes homogeneous orientation, a low molecule orientation control agent and a polymer orientation control agent can be used, for example.

As the low molecular orientation control agent, for example, paragraphs [0009] to [0083] of JP-A-2002-020363, paragraphs [0111] to [0120] of JP-A-2006-106662, and JP-A-2012 Reference may be made to the descriptions in paragraphs [0021] to [0029] of -211306, which are incorporated herein by reference.

Moreover, as an orientation control agent of a polymer, Paragraph [0021]-[0057] of Unexamined-Japanese-Patent No. 2004-198511, and Paragraph [0121]-[0167] of Unexamined-Japanese-Patent No. 2006-106662 can be referred, for example. The contents of which are incorporated herein by reference.

Moreover, as an orientation control agent which forms or promotes homeotropic orientation, a boronic acid compound and an onium salt compound are mentioned, for example, Specifically, Unexamined-Japanese-Patent No. 2008-225281 is a paragraph. , Japanese Patent Application Laid-Open No. 2012-208397, paragraphs [0052] to [0058], Japanese Patent Application Laid-Open No. 2008-026730, and Japanese Patent Application Laid-Open No. 2016-193869. Reference may be made to compounds described in paragraphs and the like, which are incorporated herein by reference.

On the other hand, cholesteric orientation can be implement | achieved by adding a chiral agent to the polymeric composition of this invention, and the rotation direction of cholesteric orientation can be controlled by the chirality direction. Moreover, the pitch of cholesteric orientation can be controlled by the orientation regulation force of a chiral agent.

It is preferable that it is 0.01-10 mass% with respect to the total solid mass in a polymeric liquid crystal composition, and, as for content in the case of containing an orientation control agent, it is more preferable that it is 0.05-5 mass%. When content is this range, there exists no precipitation, phase separation, an orientation defect, etc., realizing a desired orientation state, and the optically anisotropic film which is uniform and high in transparency can be obtained.

These orientation control agents can also provide a polymerizable functional group, especially the polymerizable liquid crystal compound which comprises the polymeric liquid crystal composition of this invention, and the polymerizable functional group which can superpose | polymerize.

[UV absorber]

The polymeric liquid crystal composition of this invention may contain the ultraviolet absorber represented by following formula (5).

Moreover, it is preferable that the maximum absorption wavelength A of the polymeric liquid crystal compound represented by said Formula (1), and the maximum absorption wavelength B of the ultraviolet absorber represented by following formula (5) satisfy | fill following formula (6).

Here, in this specification, maximum absorption wavelength refers to the absorption wavelength of the longest wavelength side of the peak which exists in the wavelength range of 300-400 nm, and when an absorption spectrum shows a bimodal peak, The absorption on the long wavelength side is taken as the maximum absorption wavelength.

[Formula 10]

0nm≤A-B <24nm … (6)

In said formula (5), Ar represents the aromatic hydrocarbon ring or aromatic heterocycle which may have a substituent.

Here, as an aromatic hydrocarbon ring, aryl groups, such as a phenyl group, 2, 6- diethylphenyl group, a naphthyl group, are mentioned, for example.

Moreover, as an aromatic heterocycle, heteroaryl groups, such as a thienyl group, a thiazolyl group, a furyl group, a pyridyl group, are mentioned, for example.

Moreover, as a substituent which Ar may have, an alkyl group, an alkoxy group, a halogen atom, etc. are mentioned, for example.

As an alkyl group, a C1-C18 linear, branched or cyclic alkyl group is preferable, for example, A C1-C8 alkyl group (for example, a methyl group, an ethyl group, a propyl group, an isopropyl group, n-butyl group) is preferable. , Isobutyl group, sec-butyl group, t-butyl group, cyclohexyl group, etc.) are more preferable, It is more preferable that it is a C1-C4 alkyl group, It is especially preferable that it is a methyl group or an ethyl group.

As an alkoxy group, a C1-C18 alkoxy group is preferable, for example, and a C1-C8 alkoxy group (for example, a methoxy group, an ethoxy group, n-butoxy group, a methoxyethoxy group, etc.) is more preferable. It is more preferable that it is a C1-C4 alkoxy group, and it is especially preferable that it is a methoxy group or an ethoxy group.

As a halogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom etc. are mentioned, for example, Especially, it is preferable that they are a fluorine atom and a chlorine atom.

In the formula (5), X represents a carbon atom or a nitrogen atom, Y represents an oxygen atom or a nitrogen atom, Z represents an oxygen atom or a nitrogen atom, and X, Y and Z each represent You may have a substituent and the substituent which X and the substituent which Y has may combine with each other, and may form the ring containing X and Y. However, the bond form of X and Y may be a double bond or a triple bond by the presence or absence of the substituent of Y.

Examples of the substituent which X, Y and Z may have include the same substituents as the substituent which Ar may have.

As an ultraviolet absorber represented by said Formula (5), the compound of Paragraph [0018]-[0031] of Unexamined-Japanese-Patent No. 2007-072163 is mentioned, for example, Specifically, the same publication- ] The compound described in a paragraph is mentioned.

In addition, as a ultraviolet absorber represented by said Formula (5), the triazine type compound of Paragraph-of the Unexamined-Japanese-Patent No. 2013-082707 is also mentioned, for example.

As the ultraviolet absorber represented by the above formula (5), Tinuvin400, Tinuvin405, Tinuvin460, Tinuvin477, Tinuvin479, and Tinuvin1577 (all manufactured by BASF) can be used as commercially available products.

In the present invention, for the reason that the light resistance of the optically anisotropic film formed is good, the content in the case of containing the ultraviolet absorber represented by the formula (5) is 1 to the content of the polymerizable liquid crystal compound represented by the formula (1). It is preferable that it is -20 mass%.

Although the reason why light resistance becomes good is not clear, when the maximum absorption wavelength A of a polymeric liquid crystal compound and the maximum absorption wavelength B of an ultraviolet absorber satisfy | fill said Formula (6), the absorption wavelength of a polymeric liquid crystal compound and an ultraviolet absorber will be It is estimated that there are many overlapping regions and energy transfer to a ultraviolet absorber from a polymerizable liquid crystal compound is likely to occur. As a result, decomposition | disassembly of a polymeric liquid crystal compound is suppressed and it is guessed that the light resistance of an optically anisotropic film improves.

[Optical anisotropic film]

The optically anisotropic film of this invention is an optically anisotropic film obtained by superposing | polymerizing the polymeric liquid crystal composition of this invention mentioned above.

As a formation method of an optically anisotropic film, the method of immobilizing by superposition | polymerization, for example using the polymeric liquid crystal composition of this invention mentioned above after making it into a desired orientation state is mentioned.

Here, although polymerization conditions are not specifically limited, In superposition | polymerization by light irradiation, it is preferable to use an ultraviolet-ray. It is preferable that irradiation amount is 10mJ / cm <^2> -50J / cm <^2> , It is more preferable that it is 20mJ / cm <^2> -5J / cm <^2> , It is more preferable that it is 30mJ / cm <^2> -3J / cm <^2> , 50-1000mJ It is particularly preferable that it is / cm ² . Moreover, in order to accelerate a polymerization reaction, you may carry out under heating conditions.

In addition, in this invention, an optically anisotropic film can be formed on the arbitrary support body in the optical film of this invention mentioned later, or on the polarizer in the polarizing plate of this invention mentioned later.

In the present invention, for the reason that the contrast ratio in an image display device, especially a liquid crystal display device is improved, the optically anisotropic film is polymerized (fixed orientation) after the polymerizable liquid crystal composition of the present invention is oriented on a smectic phase. It is preferable that it is a film | membrane obtained.

This is considered to be because the smectic phase is higher in order than the nematic phase and scattering due to the orientation disturbance of the optically anisotropic layer is suppressed. In addition, whether an optically anisotropic film shows a smectic phase can be judged according to whether or not it has a periodic structure by X-ray diffraction. For example, the presence or absence of a periodic structure can be confirmed by analyzing a diffraction pattern with the thin-film X-ray-diffraction apparatus ATXG (made by Rigaku Corporation).

It is preferable that it is a positive A plate or a positive C plate, and, as for the optically anisotropic film of this invention, it is more preferable that it is a positive A plate.

Here, the positive A plate (positive A plate) and the positive C plate (positive C plate) are defined as follows.

Positive A plate when nx and the refractive index of the direction orthogonal in the plane orthogonal slow axis and nx and the refractive index of the thickness direction are set to nx for the refractive index of the slow axis direction (direction in which the refractive index becomes largest in surface) in a film plane, Is to satisfy the relationship of formula (A1), and positive C plate is to satisfy the relationship of formula (C1). In addition, the positive A plate has a positive value of Rth and the positive C plate has a negative value of Rth.

Formula (A1) nx> ny ≒ nz

Formula (C1) nz> nx ≒ ny

In addition, the above-mentioned "≒" includes not only the case where both are completely the same, but also the case where both are substantially the same.

In a positive A plate, "substantially the same" also means that (ny-nz) xd (where d is the thickness of the film) is -10 to 10 nm, preferably -5 to 5 nm. ny_nz ", and (nx-nz) xd is included in" nx_nz "also when -10-10 nm, Preferably it is -5-5 nm. Moreover, in a positive C plate, when (nx-ny) xd (where d is thickness of a film) is 0-10 nm, Preferably 0-5 nm is included in "nx_ny", for example. .

When the optically anisotropic film of the present invention is a positive A plate, from the viewpoint of functioning as a λ / 4 plate, it is preferable that Re (550) is 100 to 180 nm, more preferably 120 to 160 nm, and still more preferably 130 to 150 nm. It is preferable and it is especially preferable that it is 130-140 nm.

Here, the "λ / 4 plate" is a plate having a? / 4 function, and specifically, a plate having a function of converting linearly polarized light of a specific wavelength into circularly polarized light (or circularly polarized light into linearly polarized light).

[Optical film]

The optical film of this invention is an optical film which has the optically anisotropic film of this invention.

1A, 1B, and 1C (hereinafter, abbreviated as "Fig. 1" when these drawings do not require distinction) are schematic cross-sectional views each showing an example of the optical film of the present invention.

1 is a schematic diagram, and the relationship, positional relationship, etc. of the thickness of each layer do not necessarily correspond with an actual thing, The support body, the oriented film, and the hard-coat layer which are shown in FIG. 1 are arbitrary structural members.

The optical film 10 shown in FIG. 1 has the support body 16, the orientation film 14, and the optically anisotropic film 12 in this order.

In addition, as shown in FIG. 1B, the optical film 10 may have a hard coat layer 18 on the side opposite to the side on which the alignment film 14 of the support 16 is provided, as shown in FIG. 1C. You may have the hard-coat layer 18 on the opposite side to the side in which the alignment film 14 of the optically anisotropic film 12 was provided.

Hereinafter, the various members used for the optical film of this invention are demonstrated in detail.

[Optical anisotropic film]

The optically anisotropic film which the optical film of this invention has is the optically anisotropic film of this invention mentioned above.

In the optical film of this invention, although it does not specifically limit about the thickness of the said optically anisotropic film, It is preferable that it is 0.1-10 micrometers, and it is more preferable that it is 0.5-5 micrometers.

[Support]

As above-mentioned, the optical film of this invention may have a support body as a base material for forming an optically anisotropic film.

It is preferable that such a support body is transparent, and it is preferable that specifically, light transmittance is 80% or more.

As such a support body, a glass substrate and a polymer film are mentioned, for example, As a material of a polymer film, Cellulose-type polymer; Acrylic polymer which has acrylic acid ester polymers, such as a polymethyl methacrylate and a lactone ring containing polymer; Thermoplastic norbornene-based polymers; Polycarbonate-based polymers; Polyester-based polymers such as polyethylene terephthalate and polyethylene naphthalate; Styrene polymers such as polystyrene and acrylonitrile styrene copolymer (AS resin); Polyolefin polymers such as polyethylene, polypropylene, and ethylene-propylene copolymers; Vinyl chloride polymers; Amide polymers such as nylon and aromatic polyamides; Imide-based polymers; Sulfone-based polymers; Polyether sulfone-based polymers; Polyether ether ketone polymers; Polyphenylene sulfide-based polymers; Vinylidene chloride polymers; Vinyl alcohol-based polymers; Vinyl butyral polymers; Arylate polymers; Polyoxymethylene type polymers; Epoxy type polymer or the polymer which mixed these polymers is mentioned.

Moreover, the aspect which the polarizer mentioned later also serves as such a support body may be sufficient.

Although it does not specifically limit about the thickness of the said support body in this invention, It is preferable that it is 5-60 micrometers, and it is more preferable that it is 5-30 micrometers.

[Alignment film]

When the optical film of this invention has arbitrary supporters mentioned above, it is preferable to have an orientation film between a support body and an optically anisotropic film. Moreover, the aspect which the support body mentioned above doubles as an oriented film may be sufficient.

The alignment film generally contains a polymer as a main component. As a polymer material for oriented films, it has described in many documents, and many commercial items can be obtained.

As the polymer material used in the present invention, polyvinyl alcohol or polyimide and derivatives thereof are preferable. Especially modified or unmodified polyvinyl alcohol is preferable.

As an orientation film which can be used for this invention, For example, the orientation film as described in page 43, line 24-page 49, line of international publication 01/088574; Modified polyvinyl alcohol according to paragraphs [0071] to [0095] of Japanese Patent Publication No. 3907735; The liquid crystal aligning film formed with the liquid crystal aligning agent of Unexamined-Japanese-Patent No. 2012-155308, etc. are mentioned.

In this invention, it is also preferable to use a photo-alignment film as an orientation film because it becomes possible to prevent surface deterioration by not contacting the surface of an orientation film at the time of formation of an orientation film.

Although it does not specifically limit as a photo-alignment film, Polymer materials, such as the polyamide compound and polyimide compound of Paragraph [0024]-[0043] of International Publication No. 2005/096041; Liquid crystal aligning film formed of the liquid crystal aligning agent which has the photo-alignment machine of Unexamined-Japanese-Patent No. 2012-155308; Trade name LPP-JP265CP manufactured by Rolic Technologies, Inc. may be used.

Moreover, in this invention, although the thickness of the said oriented film is not specifically limited, It is preferable that it is 0.01-10 micrometers from a viewpoint of alleviating the surface asperity which may exist in a support body, and forming the optically anisotropic film of uniform film thickness, and it is 0.01- It is more preferable that it is 1 micrometer, and it is still more preferable that it is 0.01-0.5 micrometer.

[Hard coat layer]

It is preferable that the optical film of this invention has a hard-coat layer in order to provide the physical strength of a film. Specifically, the hard coat layer may be provided on the side opposite to the side on which the alignment film of the support is provided (see FIG. 1B), or may have the hard coat layer on the side opposite to the side on which the alignment film of the optically anisotropic film is provided (FIG. 1C). Reference).

As the hard coat layer, those described in paragraphs [0190] to [0196] of JP2009-098658A can be used.

[Other optically anisotropic film]

The optical film of this invention may have another optically anisotropic film separately from the optically anisotropic film of this invention.

That is, the optical film of this invention may have a laminated structure of the optically anisotropic film of this invention, and another optically anisotropic film.

Such another optically anisotropic film is not specifically limited as long as it does not mix | blend the polymeric liquid crystal compound represented by said Formula (1), and is obtained using the other polymeric compound (especially liquid crystal compound) mentioned above.

Here, generally, a liquid crystal compound can be classified into a rod-shaped type and a disk-shaped type from the shape. In addition, there are low molecular and high polymer types, respectively. A polymer generally refers to a polymer having a degree of polymerization of 100 or more (polymer physics-phase transition dynamics, Toi Masao, p. 2, Iwanami Shoten, 1992). In the present invention, any liquid crystal compound can be used, but it is preferable to use a rod-like liquid crystal compound or a discotic liquid crystal compound (a discotic liquid crystal compound). You may use 2 or more types of rod-like liquid crystal compounds, 2 or more types of discotic liquid crystal compounds, or a mixture of a rod-like liquid crystal compound and a discotic liquid crystal compound. In order to fix the above-mentioned liquid crystal compound, it is more preferable to form using the rod-shaped liquid crystal compound or disk shaped liquid crystal compound which has a polymeric group, and it is more preferable that a liquid crystal compound has two or more polymeric groups in 1 molecule. When a liquid crystal compound is a mixture of two or more types, it is preferable that at least 1 type of liquid crystal compound has two or more polymerizable groups in 1 molecule.

As a rod-shaped liquid crystal compound, the thing of Claim 1 of Unexamined-Japanese-Patent No. 11-513019, and Paragraph [0026]-[0098] of Unexamined-Japanese-Patent No. 2005-289980 can be used preferably, As a discotic liquid crystal compound, for example, For example, Paragraph [0020]-[0067] of Unexamined-Japanese-Patent No. 2007-108732 and Paragraph-[0013]-[0108] of Unexamined-Japanese-Patent No. 2010-244038 can be used preferably, However, it is not limited to these. Do not.

[Polarizing Plate]

The polarizing plate of this invention has the optical film and polarizer of this invention mentioned above.

Moreover, the polarizing plate of this invention can be used as a circularly polarizing plate, when the optically anisotropic film of this invention mentioned above is (lambda) / 4 plate (positive A plate).

Moreover, in the polarizing plate of this invention, when the optically anisotropic film of this invention mentioned above is a (lambda) / 4 plate (positive A plate), the angle which the slow axis of a (lambda) / 4 plate and the absorption axis of the polarizer mentioned later make 30-60 degrees It is preferable that it is, It is more preferable that it is 40-50 degrees, It is more preferable that it is 42-48 degrees, It is especially preferable that it is 45 degrees.

Here, the "ground axis" of the λ / 4 plate means the direction in which the refractive index is maximum in the plane of the λ / 4 plate, and the "absorption axis" of the polarizer means the direction with the highest absorbance.

[Polarizer]

The polarizer of the polarizing plate of the present invention is not particularly limited as long as it is a member having a function of converting light into specific linearly polarized light, and conventionally known absorbing polarizers and reflective polarizers can be used.

As the absorption polarizer, an iodine polarizer, a dye polarizer using a dichroic dye, a polyene polarizer, or the like is used. The iodine-based polarizer and the dye-based polarizer include a coating type polarizer and a stretched type polarizer, and both can be applied. However, a polarizer produced by adsorbing iodine or a dichroic dye to polyvinyl alcohol and stretching them is preferable.

Moreover, as a method of obtaining a polarizer by extending | stretching and dyeing in the laminated | multilayer film state which formed the polyvinyl alcohol layer on the base material, Unexamined-Japanese-Patent No. 5048120, Unexamined-Japanese-Patent No. 5,514,18, Japan Patent No. 4471205, Japan And Japanese Patent No. 4,477,148 and Japanese Patent No. 4,472,86. The well-known technique regarding these polarizers can also be used preferably.

As a reflective polarizer, the polarizer which laminated | stacked the thin film which differs birefringence, the wire grid polarizer, the polarizer which combined the cholesteric liquid crystal which has a selective reflection range, and a quarter wave plate, etc. are used.

Among them, from the viewpoint of better adhesion, a polymer containing polyvinyl alcohol-based resin (-CH ₂ -CHOH- as a repeating unit, in particular, at least one selected from the group consisting of polyvinyl alcohol and ethylene-vinyl alcohol copolymer It is preferable that it is a polarizer containing).

Although the thickness of a polarizer is not specifically limited in this invention, It is preferable that it is 3 micrometers-60 micrometers, It is more preferable that it is 5 micrometers-30 micrometers, It is more preferable that it is 5 micrometers-15 micrometers.

[Adhesive layer]

In the polarizing plate of the present invention, an adhesive layer may be disposed between the optically anisotropic film and the polarizer in the optical film of the present invention.

As an adhesive layer used for lamination | stacking an optically anisotropic film and a polarizer, the ratio (tan-delta = G "/ G ') of storage elastic modulus G' and loss elastic modulus G" measured by the dynamic viscoelasticity measuring apparatus, for example is 0.001-1.5 A phosphorus substance is shown and what is called an adhesive, a substance which is easy to creep, etc. are contained. As an adhesive which can be used for this invention, although a polyvinyl alcohol-type adhesive is mentioned, it is not limited to this, for example.

[Image display device]

The image display apparatus of this invention is an image display apparatus which has the optical film of this invention or the polarizing plate of this invention.

The display element used for the image display apparatus of this invention is not specifically limited, For example, a liquid crystal cell, organic electroluminescent (it abbreviates as "EL") display panel, a plasma display panel, etc. are mentioned.

Among these, it is preferable that it is a liquid crystal cell and an organic electroluminescent display panel, and it is more preferable that it is a liquid crystal cell. That is, as the image display apparatus of this invention, it is preferable that it is a liquid crystal display device using a liquid crystal cell as a display element, and an organic electroluminescence display using the organic electroluminescence display panel as a display element, and it is more preferable that it is a liquid crystal display device.

[Liquid crystal display device]

The liquid crystal display device which is an example of the image display device of this invention is a liquid crystal display device which has the polarizing plate of this invention mentioned above, and a liquid crystal cell.

Moreover, in this invention, it is preferable to use the polarizing plate of this invention as a polarizing plate of a front side among the polarizing plates provided in both sides of a liquid crystal cell, and it is more preferable to use the polarizing plate of this invention as a polarizing plate of a front side and a rear side. .

Below, the liquid crystal cell which comprises a liquid crystal display device is demonstrated in detail.

<Liquid crystal cell>

The liquid crystal cell used for the liquid crystal display device is preferably a VA (Vertical Alignment) mode, an OCB (Optically Compensated Bend) mode, an In-Plane-Switching (IPS) mode, or TN (Twisted Nematic), but is not limited thereto. It is not.

In the liquid crystal cell of TN mode, rod-shaped liquid crystalline molecules are substantially horizontally oriented at the time of no voltage application, and are twistingly oriented at 60 to 120 °. The liquid crystal cell of TN mode is most used as a color TFT liquid crystal display device, and many documents have description.

In the liquid crystal cell of VA mode, rod-shaped liquid crystalline molecules are orientated substantially vertically when voltage is not applied. In the liquid crystal cell of VA mode, (1) VA mode liquid crystal cell which aligns rod-shaped liquid crystalline molecules substantially vertically when no voltage is applied, and is substantially horizontally aligned when voltage is applied. In addition to 2-176625, (2) a liquid crystal cell (SID97, Digest of tech.Papers) (multiple domain of VA mode) in which the VA mode is multi-domain (in order to increase the viewing angle) 28 ( 1997) 845), (3) A liquid crystal cell (n-ASM mode) of a liquid crystal cell (n-ASM mode) in which the rod-shaped liquid crystalline molecules are substantially vertically aligned when no voltage is applied and torsional multi-domain alignment when a voltage is applied 58 to 59 (1998)) and (4) liquid crystal cells in SURVIVAL mode (presented by LCD International 98). In addition, any of a patterned vertical alignment (PVA) type, an optical alignment type, and a polymer-sustained alignment (PSA) may be used. Details of these modes are described in JP-A-2006-215326 and JP-A-2008-538819.

In the liquid crystal cell of the IPS mode, the rod-shaped liquid crystal molecules are oriented substantially parallel to the substrate, and the liquid crystal molecules respond planely by applying an electric field parallel to the substrate surface. In the IPS mode, black display is performed in the state where no electric field is applied, and the absorption axes of the upper and lower pairs of polarizing plates are perpendicular to each other. The method of reducing the leakage light at the time of black display in an inclination direction using an optical compensation sheet and improving a viewing angle is Unexamined-Japanese-Patent No. 10-054982, Unexamined-Japanese-Patent No. 11-202323, Unexamined-Japanese-Patent. Japanese Patent Laid-Open No. 9-292522, Japanese Patent Laid-Open No. 11-133408, Japanese Patent Laid-Open No. 11-305217, Japanese Patent Laid-Open No. Hei 10-307291 and the like.

[Organic EL display device]

As an organic electroluminescence display which is an example of the image display apparatus of this invention, For example, from a visual recognition side, it uses a polarizer, the (lambda) / 4 plate (positive A plate) which consists of the optically anisotropic film of this invention, and an organic electroluminescence display panel The aspect which has in order is mentioned suitably.

Moreover, an organic electroluminescence display panel is a display panel comprised using the organic electroluminescent element formed by sandwiching an organic light emitting layer (organic electro luminescence layer) between electrodes (between an anode and an anode). The configuration of the organic EL display panel is not particularly limited, and a known configuration is adopted.

Example

The present invention will be described in more detail based on Examples. The materials, usage amounts, ratios, treatment contents, treatment procedures and the like shown in the following examples can be appropriately changed without departing from the spirit of the present invention. Therefore, the scope of the present invention should not be limitedly interpreted by the Example shown below.

[Synthesis of Compound (I-1a)]

For the synthesis of compound (I-1a) represented by the following formula (I-1a), malononitrile, carbon disulfide and benzoquinone with reference to the method described in Justus Liebigs Annalen der Chemie, 726, 103-109 (1969) Synthesized from

[Formula 11]

Synthesis of Compound (II-1a)

The synthesis of Compound (II-1a) represented by the following Formula (II-1a) was performed by the method described in paragraph (Example 15) of JP-A-2016-081035.

[Formula 12]

Synthesis of Compound (I-1c)

[Formula 13]

As shown in the scheme, 10.0 g (39.3 mmol) of compound (I-1b), 50 ml of N, N-dimethylacetamide (DMAc), 8.0 g (78.6 mmol) of triethylamine, and 2,6-di- 433 mg of t-butyl-4-methylphenol were mixed at room temperature (23 ° C.).

9.61 g (43.2 mmol) of 4-methylsulfonyloxy butyl acrylate was added to the mixture, and it stirred at 100 degreeC for 5 hours. After cooling to room temperature, 30 ml of 1N hydrochloric acid and 50 ml of toluene were added, followed by separating liquid at 40 ° C after stirring. The organic layer was washed sequentially with 5% aqueous sodium hydrogen carbonate solution, 1% aqueous sodium hydrogen carbonate solution and 1% aqueous sodium hydrogen carbonate solution, and then 20 mg of 2,2,6,6-tetramethylpiperidine-1-oxyl (TEMPO) After the addition, the solvent was distilled off under reduced pressure. The residue was recrystallized from ethanol / toluene / n-hexane to give 4.78 g (12.6 mmol) of carboxylic acid derivatives (I-1c) (yield 32%). Moreover, all the water layers at the time of liquid separation were collected, and hydrochloric acid was dripped until the liquid became acidic, and the unreacted compound (I-1b) was precipitated and filtered. 1.6 g of compounds (I-1b) were collect | recovered by adding this crude product to 10 ml of acetone and filtering after 30 minutes of stirring (recovery rate 16%).

¹ H-NMR (Nuclear Magnetic Resonance) of the obtained compound (I-1c) is shown below.

¹ H-NMR (solvent: CDCl ₃ ) δ (ppm): 1.0-1.1 (m, 6H), 1.3-1.5 (m, 4H), 1.7-1.8 (m, 8H), 2.0-2.1 (m, 4H) , 2.2 (tt, 1H), 2.2 (tt, 1H), 4.1 (t, 2H), 4.2 (t, 2H), 5.8 (dd, 1H), 6.1 (dd, 1H), 6.4 (dd, 1H)

Synthesis of Compound (I-1d)

[Formula 14]

As shown in the scheme, 10.0 g (39.3 mmol) of compound (I-1b), 100 ml of ethyl acetate (EA), 18.2 ml of N, N-dimethylacetamide (DMAc), and 2,6-di-t- 433 mg of butyl-4-methylphenol were mixed at room temperature, and internal temperature was cooled to 5 degreeC. 6.24 ml (86.5 mmol) of thionyl chloride (SOCl ₂ ) was added dropwise to the mixture so that the internal temperature did not rise above 10 ° C. After stirring at 5 ° C. for 1 hour, 6.77 g (39.3 mmol) of 6-hydroxyhexyl acrylate was added. 37.7 ml (216 mmol) of N, N- diisopropylethylamine (DIPEA) were dripped, and it stirred at room temperature for 2 hours. After stirring, 100 ml of 1N hydrochloric acid was added to stop the reaction, and liquid separation was performed. The organic layer was washed with 10% brine, dried over magnesium sulfate, 20 mg of 2,2,6,6-tetramethylpiperidine-1-oxyl (TEMPO) was added, and then the solvent was evaporated under reduced pressure. The obtained crude product was purified by silica gel column chromatography to obtain 4.66 g (11.4 mmol) of compound (I-1d) (yield 29%).

¹ H-NMR of the obtained compound (I-1d) is shown below.

¹ H-NMR (solvent: CDCl ₃ ) δ (ppm): 0.9-1.1 (m, 6H), 1.3-1.5 (m, 8H), 1.6-1.7 (m, 4H), 2.0-2.1 (m, 4H) , 2.2 (tt, 1H), 2.3 (tt, 1H), 4.0 (t, 2H), 4.2 (t, 2H), 5.8 (dd, 1H), 6.1 (dd, 1H), 6.4 (dd, 1H)

Synthesis of Compound (I-1e)

[Formula 15]

As shown in the scheme, 10.0 g (39.3 mmol) of compound (I-1b), 100 ml of ethyl acetate (EA), 18.2 ml of N, N-dimethylacetamide (DMAc), and 2,6-di-t- 433 mg of butyl-4-methylphenol were mixed at room temperature, and internal temperature was cooled to 5 degreeC. 6.24 ml (86.5 mmol) of thionyl chloride (SOCl ₂ ) was added dropwise to the mixture so that the internal temperature did not rise above 10 ° C. After stirring at 5 ° C. for 1 hour, 6.77 g (39.3 mmol) of 5-hydroxy-3-methylpentylacrylate was added. 37.7 ml (216 mmol) of N, N- diisopropylethylamine (DIPEA) were dripped, and it stirred at room temperature for 2 hours. After stirring, 100 ml of 1N hydrochloric acid was added to stop the reaction, and liquid separation was performed. The organic layer was washed with 10% brine, dried over magnesium sulfate, 20 mg of 2,2,6,6-tetramethylpiperidine-1-oxyl (TEMPO) was added, and then the solvent was evaporated under reduced pressure. The obtained crude product was purified by silica gel column chromatography to obtain 4.02 g (9.83 mmol) of compound (I-1e) (yield 25%).

¹ H-NMR of the obtained compound (I-1e) is shown below.

¹ H-NMR (solvent: CDCl ₃ ) δ (ppm): 0.9 (s, 3H), 1.0-1.1 (m, 6H), 1.3-1.5 (m, 4H), 1.5-1.6 (m, 1H), 1.6 -1.8 (m, 8H), 1.9-2.1 (m, 4H), 2.2 (tt, 1H), 2.2 (tt, 1H), 4.0-4.2 (m, 2H), 4.2-4.3 (m, 2H), 5.8 (dd, 1H), 6.1 (dd, 1H), 6.4 (dd, 1H)

Synthesis of Compound (I-1f)

[Formula 16]

As shown in the scheme, 10.0 g (39.3 mmol) of compound (I-1b), 30 ml of N, N-dimethylacetamide (DMAc), 10 ml of toluene, 7.96 g (78.6 mmol) of triethylamine, and 2,6 100 mg of -di-t-butyl-4-methylphenol were mixed at room temperature (23 ° C).

8.40 g (43.2 mmol) of 2-methylsulfonyloxyethyl acrylates were added to the mixture, and it stirred at 90 degreeC for 5 hours. After cooling to room temperature, a mixed solution of 2.60 g of concentrated hydrochloric acid and 20 ml of water was added thereto, followed by stirring at 40 ° C.

Subsequently, 20 ml of toluene and 30 ml of 5% sodium hydrogencarbonate aqueous solution were added to the organic layer, and the liquid separation was performed after stirring at 40 degreeC.

Subsequently, the organic layer was washed twice with 30 ml of a 1% aqueous sodium hydrogen carbonate solution, and then 20 mg of 2,2,6,6-tetramethylpiperidine-1-oxyl (TEMPO) was added, and then the solvent was distilled off under reduced pressure. . Subsequent purification was not performed, and the toluene solution of compound (I-1f) was used for the next step as it was. In terms of NMR and HPLC (High Performance Liquid Chromatography), the body content was 28% and the yield was 45%.

Synthesis of Compound (I-1g)

[Formula 17]

As shown in the above scheme, in place of 2-methylsulfonyloxyethyl acrylate, except for using a mixture of 2-methylsulfonyloxypropyl acrylate and 1-methylsulfonyloxypropyl acrylate, the compound (I- In the same manner as in 1f), the compound (I-1g) was synthesized.

Synthesis of Mixture (I-1h)

[Formula 18]

As shown in the scheme, instead of 2-methylsulfonyloxyethyl acrylate, 4-methylsulfonyloxybutyl acrylate and 2-methylsulfonyloxyethyl acrylate are used except for mixing and using the compound (I-1f). In the same manner as), a mixture (I-1h) was synthesized. 2-methylsulfonyloxybutyl acrylate and 2-methylsulfonyloxyethyl acrylate were used at a molar ratio of 95: 5.

Example 1

Synthesis of Compound (I-1-4)

[Formula 19]

As shown in the scheme, 2.53 g (6.65 mmol) of compound (I-1c), 12.6 ml of toluene, 3.80 ml of N, N-dimethylacetamide (DMAc), and 2,6-di-t-butyl-4 33 mg of methylphenol were mixed at room temperature, and the internal temperature was cooled to 5 ° C. The mixture, thionyl chloride (SOCl ₂₎ 0.58ml (7.98mmol) was added dropwise so as not to increase the internal temperature of at least 10 ℃. After stirring at 5 ° C for 1 hour, 0.75 g (3.02 mmol) of tetrahydrofuran (THF) solution (12.6 ml) was added. 2.90 ml (16.6 mmol) of N, N- diisopropylethylamine (DIPEA) were dripped, and it stirred at room temperature for 2 hours. After stirring, 10 ml of 1N hydrochloric acid and 10 ml of ethyl acetate were added to stop the reaction, and liquid separation was performed. After the organic layer was washed with 10% saline, 15 ml of isopropanol and 10 ml of methanol were added dropwise in that order, and then cooled to 5 ° C to precipitate precipitated crystals.

The obtained crude product was purified by silica gel column chromatography to obtain 2.79 g (2.87 mmol) of compound (I-1-4) (yield 95%).

¹ H-NMR of the obtained compound (I-1-4) is shown below.

¹ H-NMR (solvent: CDCl ₃ ) δ (ppm): 1.0-1.2 (m, 12H), 1.3-1.5 (m, 4H), 1.5-1.6 (m, 4H), 1.7-1.8 (m, 8H) , 1.8-2.0 (m, 8H), 2.0-2.1 (m, 4H), 2.1-2.2 (m, 4H), 2.2 (tt, 2H), 2.5 (tt, 2H), 4.1 (t, 4H), 4.2 (t, 4H), 5.8 (dd, 2H), 6.1 (dd, 2H), 6.4 (dd, 2H), 7.3 (s, 2H)

Example 2

Synthesis of Compound (I-1-5)

[Formula 20]

As shown in the scheme, 0.91 g (2.22 mmol) of compound (I-1d), 4.53 ml of ethyl acetate (EA), 1.36 ml of N, N-dimethylacetamide (DMAc), and 2,6-di-t 11 mg of -butyl-4-methylphenols were mixed at room temperature, and internal temperature was cooled to 5 degreeC. The mixture, thionyl chloride (SOCl ₂₎ 0.19ml (2.66mmol) was added dropwise so as not to increase the internal temperature of at least 10 ℃. After stirring at 5 ° C. for 1 hour, 0.25 g (1.01 mmol) of THF solution (5.00 ml) of compound (I-1a) was added. 0.97 ml (5.54 mmol) of N, N-diisopropylethylamine (DIPEA) was dripped, and it stirred at room temperature for 2 hours. After stirring, 10 ml of 1N hydrochloric acid and 10 ml of ethyl acetate were added to stop the reaction, and liquid separation was performed. The organic layer was washed with 10% brine, dried over magnesium sulfate, and the solvent was distilled off under reduced pressure. The obtained crude product was purified by silica gel column chromatography to obtain 0.96 g (0.94 mmol) of compound (I-1-5) (yield 93%).

¹ H-NMR of the obtained compound (I-1-5) is shown below.

¹ H-NMR (solvent: CDCl ₃ ) δ (ppm): 1.0-1.2 (m, 12H), 1.3-1.5 (m, 12H), 1.5-1.6 (m, 4H), 1.6-1.7 (m, 8H) , 1.8-1.9 (m, 8H), 2.0-2.1 (m, 4H), 2.1-2.2 (m, 4H), 2.2 (tt, 2H), 2.5 (tt, 2H), 4.1 (t, 4H), 4.2 (t, 4H), 5.8 (dd, 2H), 6.1 (dd, 2H), 6.4 (dd, 2H), 7.3 (s, 2H)

Example 3

[Synthesis of Compound (I-1-6)]

[Formula 21]

As shown in the scheme, 1.09 g (2.66 mmol) of compound (I-1e), 5.43 ml of ethyl acetate (EA), 1.63 ml of N, N-dimethylacetamide (DMAc), and 2,6-di-t 13 mg of -butyl-4-methylphenols were mixed at room temperature, and internal temperature was cooled to 5 degreeC. The mixture, thionyl chloride (SOCl ₂₎ 0.23ml (3.19mmol) was added dropwise so as not to increase the internal temperature of at least 10 ℃. After stirring at 5 ° C. for 1 hour, 0.30 g (1.21 mmol) of THF solution (5.00 ml) was added to Compound (I-1a). 1.16 ml (6.65 mmol) of N, N-diisopropylethylamine (DIPEA) was dripped, and it stirred at room temperature for 2 hours. After stirring, 10 ml of 1N hydrochloric acid and 10 ml of ethyl acetate were added to stop the reaction, and liquid separation was performed. The organic layer was washed with 10% brine, dried over magnesium sulfate, and the solvent was distilled off under reduced pressure. The obtained crude product was purified by silica gel column chromatography to obtain 1.11 g (1.08 mmol) of compound (I-1-6) (yield 89%).

¹ H-NMR of the obtained compound (I-1-6) is shown below.

¹ H-NMR (solvent: CDCl ₃ ) δ (ppm): 1.0 (d, 6H), 1.0-1.2 (m, 12H), 1.3-1.5 (m, 4H), 1.5-1.6 (m, 6H), 1.7 -1.8 (m, 8H), 1.8-1.9 (m, 4H), 1.9-2.0 (m, 4H), 2.0-2.1 (m, 4H), 2.1-2.2 (m, 4H), 2.2 (tt, 2H) , 2.5 (tt, 2H), 4.1 (t, 4H), 4.2 (t, 4H), 5.8 (dd, 2H), 6.1 (dd, 2H), 6.4 (dd, 2H), 7.3 (s, 2H)

Example 4

Synthesis of Compound (II-1-4)

[Formula 22]

As shown in the scheme, 0.99 g (2.60 mmol) of compound (1-1c), 3.5 ml of toluene, 0.5 ml of N, N-dimethylformamide (DMF), 2,6-di-t-butyl-4- 13 mg of methylphenols were mixed at room temperature, and internal temperature was cooled to 5 degreeC. The mixture, thionyl chloride (SOCl ₂₎ 0.23ml (3.12mmol) was added dropwise so as not to increase the internal temperature of at least 10 ℃. After 30 minutes of stirring at 20 ° C, the separated lower layer was removed. The internal temperature was cooled to 5 ° C, and 0.31 g (1.18 mmol) of THF solution (10.0 ml) was added to compound (II-1a). 1.13 ml (6.50 mmol) of N, N-diisopropylethylamine (DIPEA) were dripped so that internal temperature might not rise to 10 degreeC or more, and it stirred at room temperature for 2 hours. After stirring, 75 ml of isopropyl alcohol and 50 ml of methanol were added dropwise to precipitate precipitated crystals. The resulting crude product was recrystallized from THF and isopropyl alcohol at 45 ° C., and then purified by silica gel column chromatography to obtain 1.06 g (1.08 mmol) of a polymerizable liquid crystal compound (I-6) (yield 91%) .

¹ H-NMR of the obtained compound (II-1-4) is shown below.

¹ H-NMR (solvent: CDCl ₃ ) δ (ppm): 1.0-1.2 (m, 12H), 1.3-1.5 (m, 4H), 1.5-1.6 (m, 4H), 1.7-1.8 (m, 8H) , 1.8-2.0 (m, 8H), 2.0-2.1 (m, 4H), 2.1-2.2 (m, 4H), 2.2 (s, 3H), 2.2 (tt, 2H), 2.5 (tt, 1H), 2.6 (tt, 1H), 4.1 (t, 4H), 4.2 (t, 4H), 5.8 (dd, 2H), 6.1 (dd, 2H), 6.4 (dd, 2H), 7.2 (s, 1H)

Example 5

[Synthesis of Compound (II-1-5)]

[Formula 23]

As shown in the scheme, 0.82 g (2.01 mmol) of compound (I-1d), 4.1 ml of ethyl acetate (EA), 1.2 ml of N, N-dimethylacetamide (DMAc), and 2,6-di-t 10 mg of -butyl-4-methylphenols were mixed at room temperature, and internal temperature was cooled to 5 degreeC. The mixture, thionyl chloride (SOCl ₂₎ 0.17ml (2.42mmol) was added dropwise so as not to increase the internal temperature of at least 10 ℃. After stirring for 1 hour at 5 ° C, 0.24 g (0.92 mmol) of a THF solution (5.0 ml) was added. 1.13 ml (6.50 mmol) of N, N-diisopropylethylamine (DIPEA) were dripped, and it stirred at room temperature for 2 hours. After stirring, 15 ml of 1N hydrochloric acid and 15 ml of ethyl acetate were added to stop the reaction, and liquid separation was performed. The organic layer was washed with 10% brine, dried over magnesium sulfate, and the solvent was distilled off under reduced pressure. The obtained crude product was purified by silica gel column chromatography to obtain 0.85 g (0.81 mmol) of compound (II-1-5) (yield 89%).

¹ H-NMR of the obtained compound (II-1-5) is shown below.

¹ H-NMR (solvent: CDCl ₃ ) δ (ppm): 1.0-1.2 (m, 12H), 1.3-1.5 (m, 12H), 1.5-1.6 (m, 4H), 1.6-1.7 (m, 8H) , 1.8-1.9 (m, 8H), 2.0-2.1 (m, 4H), 2.1-2.2 (m, 4H), 2.2 (s, 3H), 2.2 (tt, 2H), 2.5 (tt, 1H), 2.6 (tt, 1H), 4.1 (t, 4H), 4.2 (t, 4H), 5.8 (dd, 2H), 6.1 (dd, 2H), 6.4 (dd, 2H), 7.2 (s, 1H)

Example 6

[Formula 24]

As shown in the scheme, 45 g of toluene solution of compound (I-1f) (content of compound (I-1f) was 11.90 g (33.9 mmol) in terms of NMR and HPLC.), N, N-die 2.82 g of methyl formamide (DMF) and 15 mg of 2,6-di-t-butyl-4-methylphenol were mixed at room temperature, and the internal temperature was cooled to 5 ° C. The mixture, thionyl chloride (SOCl ₂₎ 4.40g (37.0mmol) was added dropwise so as not to increase the internal temperature of at least 10 ℃. After 30 minutes of stirring at 20 ° C, the separated lower layer was removed. Next, the internal temperature was cooled to 5 ° C., 3.83 g (15.4 mmol) of tetrahydrofuran (THF) solution (60 ml) was added, and N, N-diisopropylethylamine ( 5.57 g (43.2 mmol) of DIPEA) was dripped so that internal temperature might not rise to 10 degreeC or more, and it stirred at room temperature for 2 hours. After stirring, 13 ml of acetonitrile and 10 ml of N-ethylpyrrolidone were added, followed by raising the temperature to 45 ° C. Thereafter, 25 ml of water was added dropwise, followed by neutralization by adding 0.78 g of triethylamine. After separating an aqueous layer, 80 ml of acetone was added to the organic layer, and it cooled to 5 degreeC, and precipitated the crystal | crystallization. After adding 15 ml of methanol, the precipitated crystals were filtered out. The obtained crude compound was suspended in 50 ml of acetone and 30 ml of n-hexane at 30 ° C., stirred at 30 ° C. for 30 minutes, cooled to 5 ° C., and filtered to obtain 12.7 g of the compound represented by Formula (I-1-1). (13.9 mmol) was obtained (yield 90%).

Example 7

[Formula 25]

As shown in the scheme, except for using compound (II-1a) in place of compound (I-1a), in the same manner as in the synthesis of compound (I-1-1), compound (II-1-1) Synthesized.

[Examples 8 and 9]

[Formula 26]

Compound (I-1-2) was synthesized in the same manner as in the synthesis of compound (I-1-1), except that compound (I-1g) was used instead of compound (I-1f) (Example 8 ).

In addition, the synthesis of compound (I-1-1) except that compound (I-1g) is used instead of compound (I-1f) and compound (II-1a) is used instead of compound (I-1a). In the same manner as in the above, compound (II-1-2) was synthesized (Example 9).

The obtained compound was identified by ¹ H-NMR and MS.

(I-1-1) MS (m / z) = 917 ([M + H] &lt; + &gt;)

(II-1-1) MS (m / z) = 945 ([M + H] &lt; + &gt;)

(I-1-2) MS (m / z) = 931 ([M + H] &lt; + &gt;)

(II-1-2) MS (m / z) = 959 ([M + H] &lt; + &gt;)

Example 10

[Formula 27]

As shown in the scheme, 6.70 g (17.6 mmol) of compound (I-1d), 1.55 g (4.4 mmol) of compound (I-1f), 2.00 g of N, N-dimethylformamide (DMF), 25 ml of toluene, And 20 mg of 2,6-di-t-butyl-4-methylphenol were mixed at room temperature, and the internal temperature was cooled to 5 ° C. The mixture, thionyl chloride (SOCl ₂₎ 2.80g (23.5mmol) was added dropwise so as not to increase the internal temperature of at least 10 ℃. After 30 minutes of stirring at 20 ° C, the separated lower layer was removed. The internal temperature was cooled to 5 ° C, and a solution of 2.48 g (10.0 mmol) of tetrahydrofuran (THF) (35 ml) was added. 4.88 g (28.0 mmol) of N, N- diisopropylethylamine (DIPEA) was dripped so that internal temperature might not rise to 10 degreeC or more, and it stirred at room temperature for 2 hours. After stirring, 10 ml of acetonitrile and 5 ml of N-ethylpyrrolidone were added, followed by raising the temperature to 45 ° C. Next, 20 ml of water was dripped, and 0.50 g of triethylamine was added, and liquid-separation operation was performed and the water layer was removed. After adding 50 ml of acetone to the organic layer, it cooled to 5 degreeC and precipitated the crystal | crystallization. Furthermore, after adding 10 ml of methanol, the precipitated crystals were filtered out. The obtained crude mixture was suspended in 30 ml of acetone and 70 ml of n-hexane, stirred at 30 ° C. for 30 minutes, cooled to 5 ° C. and then filtered to give the above formula (I-1-4) (I-1-41) ( 8.66g of (M-1-1) which is a mixture of I-1-1) was obtained (yield 90%). As a result of HPLC measurement, the ratio of (I-1-4) / (I-1-41) / (I-1-1) was 65/31/4.

Example 11

A mixture (M-1-2) was synthesized in the same manner as the synthesis of the mixture (M-1-1) except that the introduction ratio of the compound (I-1d) and the compound (I-1f) was 98: 2. As a result of HPLC measurement, the ratio of (I-1-4) / (I-1-41) / (I-1-1) was 96/4 / <0.1.

Example 12

In place of compound (I-1d) and compound (I-1f), mixture (M-1-3) was synthesized using mixture (I-1h). As a result of HPLC measurement, the ratio of (I-1-4) / (I-1-41) / (I-1-1) was 91/9 / 0.1.

Example 13

[Formula 28]

In the same manner as in the synthesis of the mixture (M-1-1), the compound (I-1 g) is used in place of the compound (I-1 f), and the introduction ratio of the compound (I-1 d) and the compound (I-1 g) is adjusted. The mixture (M-2-1) was synthesize | combined as 95: 5. As a result of HPLC measurement, the ratio of (I-1-4) / (I-1-42) / (I-1-2) was 91/9 / 0.1.

Example 14

[Formula 29]

In the same manner as the synthesis of the mixture (M-1-1), the compound (M-3-1) was synthesized using the compound (II-1a) in place of the compound (I-1a). As a result of HPLC measurement, the ratio of (II-1-4) / (II-1-41) / (II-1-1) was 65/30/5.

Example 15

[Formula 30]

In the same manner as the synthesis of the mixture (M-2-1), the compound (M-4-1) was synthesized using the compound (II-1a) in place of the compound (I-1a). As a result of HPLC measurement, the ratio of (II-1-4) / (II-1-42) / (II-1-2) was 92/8 / 0.1.

Comparative Example 1

The compound B whose n is 1 in the following formula was synthesize | combined by the method as described in Paragraph [0161]-[0163] of Unexamined-Japanese-Patent No. 2010-084032.

[Formula 31]

Comparative Example 2

The compound (I-4) represented by following formula (I-4) was synthesize | combined by the method as described in Paragraph (Example 4) of Unexamined-Japanese-Patent No. 2016-081035.

[Formula 32]

<ClogP value>

About the polymeric liquid crystal compound synthesize | combined with Examples 1-5 and Comparative Examples 1 and 2, the ClogP value of Ar corresponded to the reverse wavelength dispersion expression part was computed by the method mentioned above. The results are shown in Table 3 below.

<Phase transition temperature>

About the polymeric liquid crystal compound synthesize | combined in Examples 1-5 and Comparative Examples 1 and 2, the phase transition temperature was measured using the polarizing microscope. The results are shown in Table 3 below.

Here, in Table 3 below, "C 136 SA 197 N> 250 I" of Example 1 has a phase transition temperature from the crystal state to the Smectic A phase is 136 ° C, and the phase transition from the Smectic A phase to the nematic phase Although the temperature is 197 degreeC and the nematic phase is shown even if it is 250 degreeC or more, it shows that superposition | polymerization co-curs simultaneously and the phase transition temperature to an isotropic liquid is not measurable, and "C 130 SA 203 N 238 I of Example 2 is shown. Indicates that the phase transition temperature from the crystal state to the smectic A phase is 130 ° C, the phase transition temperature from the smectic A phase to the nematic phase is 203 ° C, and the phase transition temperature from the nematic phase to the isotropic liquid is 238 ° C. In Example 5, "C (SA 200) 218 N 230 I" is 200 ° C in the temperature lowering process and transitions from the nematic phase to the smectic A phase, but does not show the smectic A phase in the temperature rising process, and from the crystal state to nema Transition temperature to tick phase It is 218 degreeC, and shows that the phase transition temperature from a nematic phase to an isotropic liquid is 230 degreeC, The "C 96 N 192 I" of the comparative example 1 has a phase transition temperature of 96 degreeC from a crystalline state to a nematic phase, It shows that the phase transition temperature to the isotropic liquid is 192 ° C.

[Production of optical film]

The polymeric composition (coating liquid for optically anisotropic film) which has the following composition was prepared, and it applied to the glass substrate containing the rubbing process polyimide aligning film (SE-150 by Nissan Chemical Industries, Ltd.) by spin coating. The coating film was oriented at the temperature shown in following Table 3, and the liquid crystal layer was formed. Then, it cooled to the exposure time temperature described in following Table 3, the orientation fixation by ultraviolet irradiation of 1000mJ / cm <^2> was performed, the optically anisotropic film was formed, and the optical film for wavelength dispersion measurement was obtained.

-------------------------------------------------- -------------------

Optically Anisotropic Layer Coating Liquid

-------------------------------------------------- -------------------

Polymerizable liquid crystal compound (compound shown in Table 3 below) 15.00 parts by mass

Photoinitiator (Irgacure 819, BASF Corporation make) 0.45 parts by mass

Fluorine-containing Compound A 0.12 parts by mass

Chloroform 35.00 parts by mass

-------------------------------------------------- -------------------

[Formula 33]

<Retardation>

About the produced optical film, the retardation value (Re (450)) of wavelength 450nm and the retardation value (Re (550)) of wavelength 550nm were measured using Axo Scan (OPMF-1, Optoscience company make), , Re (450) / Re (550) was calculated. The results are shown in Table 3 below.

<Light resistance>

About the produced optical film, the glass substrate was set to the xenon irradiator (SX75 made by Suga Shikenki Co., Ltd.) so that the coating film of a polymeric liquid crystal composition might be an irradiation surface, and the test which irradiated for 200 hours using the # 275 filter was done. Re (550) of the optical film after a test was measured, and light resistance was evaluated on the following references | standards. The results are shown in Table 3 below.

A: The amount of change in Re (550) after the test with respect to the initial phase difference value is less than 5% of the initial value.

B: The amount of change in Re (550) after the test with respect to the initial phase difference value is 5% or more and less than 15% of the initial value

C: amount of change in Re (550) after the test with respect to the initial phase difference value is 15% or more of the initial value

TABLE 3

From the result shown in Table 3, when the ClogP value of the reverse wavelength dispersion-expressing part (Ar) of a polymeric liquid crystal compound is larger than 3.5, it turned out that the reverse wavelength dispersion and light resistance of the optically anisotropic film formed are inferior (Comparative Example 1 ).

Moreover, even if the ClogP value of the reverse wavelength-dispersion-expressing part (Ar) of a polymeric liquid crystal compound is 3.5 or less, when the cyclohexane ring does not have a frame | skeleton connected by single bond in the long-axis direction, the inverse of the optically anisotropic film formed is formed. It turned out that wavelength dispersion is inferior (comparative example 2).

In contrast, the ClogP value of the reverse wavelength dispersion expression portion (Ar) is 3.5 or less, and the polymerizable liquid crystal having a skeleton in which cyclohexane rings are connected in a single bond in the long axis direction of the molecule around the reverse wavelength dispersion expression portion. It was found that the compound is excellent in liquid crystallinity and also has good reverse wavelength dispersion of the optically anisotropic film formed (Examples 1 to 5).

<Production of optical film>

The polymeric composition (coating liquid for optically anisotropic film) which has the following composition was prepared, and it applied to the glass substrate containing the rubbing process polyimide aligning film (SE-150 by Nissan Chemical Industries, Ltd.) by spin coating. In the same manner as in Examples 1 to 5, the alignment treatment and the orientation fixation were performed, an optically anisotropic film was formed, and an optical film for wavelength dispersion measurement was obtained. Evaluation of retardation and light resistance was performed on the conditions similar to Examples 1-5.

-------------------------------------------------- -------------------

Coating liquid for optically anisotropic film

-------------------------------------------------- -------------------

Polymerizable liquid crystal compound (compound shown in Table 4 below) 15 parts by mass

Photoinitiator (Irgacure 819, BASF Corporation make) 0.45 parts by mass

Fluorine-containing compound A 0.12 parts by mass

Cyclopentanone 35 parts by mass

-------------------------------------------------- -------------------

TABLE 4

From the result shown in the said Table 4, when ClogP value of the reverse wavelength dispersion expression part (Ar) of a polymeric liquid crystal compound is less than 3.5, it turns out that the reverse wavelength dispersion property and the light resistance of the optically anisotropic film formed are excellent.

<Synthesis of Polymer PA-1 Having a Photoalignment Group>

According to the method described in Langmuir, 32 (36), 9245-9253, (2016), it is shown below using 2-hydroxyethyl methacrylate (HEMA) (Tokyo Kasei Reagent) and the following cinnamic acid chloride derivatives. Monomer m-1 was synthesized.

Cinnamic acid chloride derivative

[Formula 34]

Monomer m-1

[Formula 35]

5 mass parts of 2-butanones were introduce | transduced as a solvent into the flask provided with the cooling tube, the thermometer, and the stirrer, and it refluxed by water bath heating, flowing 5 ml / min of nitrogen into the flask. Here, 5 mass parts of monomer m-1, 5 mass parts of cyclomer M100 (made by Daicel Corporation), 1 mass part of 2,2'- azobis (isobutyronitrile) as a polymerization initiator, and 2 as a solvent -The solution which mixed 5 mass parts of butanone was dripped for 3 hours, and also it stirred, maintaining the reflux state for 3 hours. After the completion of reaction, the mixture was allowed to cool to room temperature, and 30 mass parts of 2-butanone was added and diluted to obtain a polymer solution of about 20 mass%. The obtained polymer solution was poured into a large excess of methanol to precipitate the polymer, and the recovered precipitate was filtered off, washed with a large amount of methanol, and then blow-dried at 50 ° C. for 12 hours to obtain polymer PA-1 having a photo-alignment group. Got it.

Polymer PA-1

[Formula 36]

<Production of alignment film P-3>

The coating liquid for forming the following alignment film P-3 was applied onto a triacetyl cellulose film "Z-TAC" (manufactured by FUJIFILM) commercially available on the wire bar of # 2.4 continuously. The support body in which the coating film was formed was dried for 120 second by the warm air of 140 degreeC, and the alignment film P-3 was formed by polarizing ultraviolet irradiation (10mJ / cm <^2> , using an ultrahigh pressure mercury lamp) subsequently.

-------------------------------------------------- -------------------

Coating liquid for forming alignment film P-3

-------------------------------------------------- -------------------

The polymer PA-1 100.00 parts by mass

Isopropyl Alcohol 16.50 parts by mass

Butyl acetate 1072.00 parts by mass

Methyl ethyl ketone 268.00 parts by mass

-------------------------------------------------- -------------------

<Formation of Positive A Plate A-1>

The following composition A-1 was apply | coated using the bar coater on the orientation film P-3 provided in the triacetyl cellulose film. After heating the coating film formed on the alignment film P-3 to 135 degreeC by warm air, and after cooling to 60 degreeC, the coating film is irradiated with the ultraviolet-ray of 100mJ / cm <^2> by wavelength 365nm using a high pressure mercury lamp in nitrogen atmosphere, and then continues. By irradiating 500 mJ / cm <^2> ultraviolet-rays, heating at 120 degreeC, the orientation of the liquid crystal compound was fixed, and the film A-1 containing the positive A plate A-1 was produced. Re (550) was 144 nm.

-------------------------------------------------- -------------------

Composition A-1

-------------------------------------------------- -------------------

The compound (I-1-4) 80.00 parts by mass

The following polymerizable liquid crystal compound L-3 20.00 parts by mass

The following polymerization initiator PI-1 0.50 parts by mass

Leveling agent T-1 0.20 parts by mass

Chloroform 570.00 parts by mass

-------------------------------------------------- -------------------

Polymerizable Liquid Crystal Compound L-3

[Formula 37]

Polymerization Initiator PI-1

[Formula 38]

Leveling Agent T-1

[Formula 39]

<Formation of Positive A Plate A-2>

Positive A plate A-2 was produced like positive A plate A-1 except having used following composition A-2 instead of composition A-1.

-------------------------------------------------- -------------------

Composition A-2

-------------------------------------------------- -------------------

The compound (I-1-4) 55.00 parts by mass

Compound (II-1-4) 18.00 parts by mass

The polymerizable liquid crystal compound L-3 27.00 parts by mass

The polymerization initiator PI-1 0.50 parts by mass

Leveling agent T-1 0.20 parts by mass

Chloroform 570.00 parts by mass

-------------------------------------------------- -------------------

<Formation of Positive A Plate A-5>

The positive A plate A-5 was produced similarly to the positive A plate A-1 except having used the following composition A-5 instead of the composition A-1.

-------------------------------------------------- -------------------

Composition A-5

-------------------------------------------------- -------------------

The compound (I-1-4) 80.00 parts by mass

The polymerizable liquid crystal compound L-3 20.00 parts by mass

The polymerization initiator PI-1 0.50 parts by mass

Leveling agent T-1 0.20 parts by mass

Compound UV-1 5.00 parts by mass

Chloroform 570.00 parts by mass

-------------------------------------------------- -------------------

Compound UV-1

[Formula 40]

<Formation of Positive C Plate C-1>

In the same manner as the positive C plate described in paragraph [0124] of JP-A-2015-200861, film C-1 having positive C plate C-1 on the forming branch was produced. By adjusting the film thickness, Rth (550) was set to -69 nm.

<Production of alignment film P-4>

Using a cycloolefin polymer film (COP) (ZF-14, manufactured by Nippon Xeon Co., Ltd.), using a corona treatment device (AGF-B10, manufactured by Kasuga Denki Co., Ltd.) once under the conditions of an output of 0.3 kW and a processing speed of 3 m / min. Processed. The following composition was apply | coated to the surface which corona-treated, bar coater-coated, it dries at 80 degreeC for 1 minute, and accumulated light quantity of 100mJ / cm <^2> using a polarizing UV irradiation apparatus (SPOT CURE SP-7; product made by Ushio Denki Co., Ltd.). Polarizing UV exposure was performed. It was 100 nm when the film thickness of the obtained orientation film was measured with the laser microscope (LEXT, Olympus Corporation).

-------------------------------------------------- -------------------

Coating liquid for formation of alignment film P-4

-------------------------------------------------- -------------------

The following polymers PA-10 5.0 parts by mass

Cyclopentanone 95.0 parts by mass

-------------------------------------------------- -------------------

Polymer PA-10

[Formula 41]

<Formation of Positive A Plate A-3>

A positive A plate A-3 was included in the same manner as the positive A plate A-1 except for using the alignment film P-4 provided on the cycloolefin polymer film instead of the alignment film P-3 provided in the triacetylcellulose film. Film A-3 was produced. Re (550) was 144 nm.

<Formation of Polarizing Plate>

Alkali saponification was performed on the surface of TD80UL (manufactured by FUJIFILM) which is a support. Specifically, the support is 1.5 specified, specifically, the support is immersed in a 1.5 specified sodium hydroxide aqueous solution at 55 ° C. for 2 minutes, and the taken out support is washed in a room temperature washing bath, Neutralized with sulfuric acid. Then, the support body obtained again was wash | cleaned in the water washing bath of room temperature, and also it dried by warm air of 100 degreeC.

Subsequently, a rolled polyvinyl alcohol film having a thickness of 80 µm was continuously stretched five times in an iodine aqueous solution, and the film after stretching was dried to obtain a polarizer having a thickness of 20 µm.

The obtained polarizer and the support body (TD80UL) to which alkali saponification process was performed were bonded together, Z-TAC (made by FUJIFILM) was bonded together on the other surface, and the polarizing plate 0 in which both surfaces of the polarizer were sandwiched by the film was obtained.

Next, as a relationship which shows arrangement | positioning of the slow axis of the positive A plate A-1-A-3 which were produced, and the absorption axis of a polarizer, respectively, in Table 5, the support surface of the polarizer and positive A plate of the said polarizing plate 0 was used using an adhesive. Only the positive A plate was transferred onto a polarizing plate by bonding together and peeling off the support body of the positive A plate continuously. Subsequently, only the positive C plate C-1 is bonded by bonding the application surface of the positive C plate C-1 to the surface of the positive A plate transferred using an adhesive, and peeling off the support for forming the film C-1. It transfered on plate A, and produced polarizing plates 1-6.

TABLE 5

<Mounting on organic EL display device>

GALAXY S IV by SAMSUNG Corporation with an organic EL display panel was disassembled, the circularly polarizing plate was peeled off, and the polarizing plates 1-3 produced above were bonded together on the organic EL display panel, and the organic electroluminescence display was produced.

(reflectivity)

The organic EL display device thus produced was measured in a specular component excluded (SCE) mode using a colorimeter (Konica Minolta, CM-2022), and the obtained Y values were compared based on the panel before decomposition. One organic EL display device exhibited an equivalent or lower value than the panel before decomposition and exhibited excellent black display performance with visually suppressed color tone inclusion.

<Production of liquid crystal display device>

The polarizing plate of the visual recognition side was peeled from the liquid crystal cell of iPad (trademark, Apple company), and it used as the liquid crystal cell of IPS mode. Instead of the polarizing plate peeled off, the polarizing plates 4-6 produced above were bonded together to the liquid crystal cell, and the liquid crystal display device was produced. At this time, when observed from the direction perpendicular | vertical to the liquid crystal cell board | substrate surface, it bonded together so that the absorption axis of a polarizing plate and the optical axis of the liquid crystal layer in a liquid crystal cell may become a perpendicular direction.

The obtained liquid crystal display device was excellent in the front contrast ratio and the perspective color tone at the time of black display.

<Light resistance test of positive A plate>

The obtained positive A plates A-1 and A-5 were transferred to the glass plate using an adhesive, and the support body was peeled off. The obtained laminated body was set in the xenon irradiator (SX75 made by Suga Shikenki Co., Ltd.) with the positive A plate side toward the light source side, and 290 mm of samples were removed from the light source using the # 275 filter, and the conditions were 150 W / m ² . Time surveyed. Using the spectrophotometer (brand name "UV-3150", the Shimadzu Corporation make), the absorbance change (DELTA) Abs of the absorption maximum wavelength which belongs to the reverse wavelength dispersion liquid crystal compound was measured with respect to the laminated body before and behind irradiation, respectively.

When ΔAbs of positive A plate A-1 was set to 1, ΔAbs of positive A plate A-5 was 0.9 or less, and it was found that positive A plate A-5 had particularly remarkable light resistance.

10 optical film
12 optically anisotropic film
14 alignment layer
16 support
18 hard coat floors

Claims (8)

As a polymeric liquid crystal compound represented by following formula (1),
[Formula 1]

The polymeric liquid crystal compound whose ClogP value of the group represented by Ar in said formula (1) is 3.5 or less.
In the formula (1), D ¹ and D ² each independently represent -O-, -S-, or -NR ^1- , and D ³ and D ⁴ each independently represent a single bond,- O-CO-, -C (= S ) O-, -CR 1 R 2 -, -CR 1 R 2 -CR 3 R 4 -, -O-CR 1 R 2 -, -CR 1 R 2 -O- CR ³ R ^4- , -CO-O-CR ¹ R ^2- , -O-CO-CR ¹ R ^2- , -CR ¹ R ² -O-CO-CR ³ R ^4- , -CR ¹ R ^2- CO-O-CR ³ R ^4- , -NR ¹ -CR ² R ^3- , or -CO-NR ^1- . R ¹ , R ² , R ^3, and R ⁴ each independently represent a hydrogen atom, a fluorine atom, or an alkyl group having 1 to 4 carbon atoms.
SP ¹ and SP ² each independently represent a single bond, at least one of -CH ₂ -constituting a linear or branched alkylene group having 1 to 12 carbon atoms or a linear or branched alkylene group having 1 to 12 carbon atoms; The divalent linking group substituted with -O-, -S-, -NH-, -N (Q)-, or -CO- represents a substituent. Q represents a substituent.
L ¹ and L ² each independently represent a monovalent organic group, and at least one of L ¹ and L ² represents a polymerizable group. However, when Ar is an aromatic ring represented by a following formula (Ar-3), at least ^{1 of} L <^1> and L <^2> and L <^3> and L <^4> in following formula (Ar-3) represents a polymeric group.
Ar represents any aromatic ring selected from the group consisting of groups represented by the following formulas (Ar-1) to (Ar-5).
[Formula 2]

In the formulas (Ar-1) to (Ar-5), * represents a bonding position with D ¹ or D ² .
In addition, Q ¹ represents N or CH.
In addition, Q ² represents -S-, -O- or -N (R ⁵ )-, and R ⁵ represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.
Moreover, Y <^1> represents the C6-C12 aromatic hydrocarbon group or C3-C12 aromatic heterocyclic group which may have a substituent.
Moreover, Z <^1> , Z <^2> and Z <^3> respectively independently represent a hydrogen atom, a C1-C20 monovalent aliphatic hydrocarbon group, a C3-C20 monovalent alicyclic hydrocarbon group, and a C6-C20 monovalent An aromatic hydrocarbon group, a halogen atom, a cyano group, a nitro group, -OR ⁶ , -NR ⁷ R ⁸ , or -SR ⁹ is represented, and R ⁶ to R ⁹ each independently represent a hydrogen atom or C 1 -C An alkyl group of 6 may be represented and Z ¹ and Z ² may be bonded to each other to form an aromatic ring.
In addition, A ¹ and A ² each independently represent a group selected from the group consisting of -O-, -N (R ¹⁰ )-, -S-, and -CO-, and R ¹⁰ represents a hydrogen atom or a substituent. Indicates.
Moreover, X represents the nonmetallic atom of group 14-16 which the hydrogen atom or the substituent may couple | bond.
D ⁵ and D ⁶ are each independently a single bond, -CO-O-, -C (= S) O-, -CR ¹ R ^2- , -CR ¹ R ² -CR ³ R ⁴ -,- O-CR ¹ R ^2- , -CR ¹ R ² -O-CR ³ R ^4- , -CO-O-CR ¹ R ^2- , -O-CO-CR ¹ R ^2- , -CR ¹ R ^2- O-CO-CR ³ R ^4- , -CR ¹ R ² -CO-O-CR ³ R ^4- , -NR ¹ -CR ² R ^3- , or -CO-NR ^1- . R ¹ , R ² , R ^3, and R ⁴ each independently represent a hydrogen atom, a fluorine atom, or an alkyl group having 1 to 4 carbon atoms.
In addition, each of SP ³ and SP ⁴ independently represents a single bond, a linear or branched alkylene group having 1 to 12 carbon atoms, or one of —CH ₂ — constituting a linear or branched alkylene group having 1 to 12 carbon atoms. The above has shown the bivalent coupling group substituted by -O-, -S-, -NH-, -N (Q)-, or -CO-, and Q represents a substituent.
In addition, L ³ and L ⁴ each independently represent a monovalent organic group, and at least one of L ³ and L ⁴ and L ¹ and L ² in the formula (1) represents a polymerizable group.
Moreover, Ax represents the C2-C30 organic group which has at least 1 aromatic ring selected from the group which consists of an aromatic hydrocarbon ring and an aromatic heterocycle.
Moreover, Ay represents a C2-C30 organic group which has a hydrogen atom, a C1-C12 alkyl group which may have a substituent, or at least 1 aromatic ring selected from the group which consists of an aromatic hydrocarbon ring and an aromatic heterocycle. .
Moreover, the aromatic ring in Ax and Ay may have a substituent, and Ax and Ay may combine and form the ring.
Moreover, Q <^3> represents the hydrogen atom or the C1-C6 alkyl group which may have a substituent. The method according to claim 1,
The polymerizable liquid crystal compound wherein D ¹ and D ² in the formula (1) represent -O-, and D ³ and D ⁴ represent -O-CO-. The polymeric liquid crystal composition containing the polymeric liquid crystal compound of Claim 1 or 2. The method according to claim 3,
A polymerizable liquid crystal composition further comprising a polymerizable compound having at least one polymerizable group different from the polymerizable liquid crystal compound. The optically anisotropic film obtained by superposing | polymerizing the polymeric liquid crystal composition of Claim 3 or 4. The optical film which has an optically anisotropic film of Claim 5. The polarizing plate which has an optical film of Claim 6 and a polarizer. The image display apparatus which has an optical film of Claim 6 or the polarizing plate of Claim 7.

Images